Lithium

I

LITHIUM At:l’iUAL SURVEY CO’IERIKG THE YEAR I976

EDWINM. WISER

Department of Chemistry, Missouri 65201 (U.S.A.)

University

of Xissouri-Columbia,

Columbia,

COF:TE:!TS I 2

Reviews and Books Structure and Bonding Studies Kinetics and Mechanism 3. 4_ Metalations A. At sp3 Carbon 6. At sp2 and sp Carbon and at Nitrogen Lithium Carbenoids and Other Halogen-Substituted Organolithiums 65: Addition and Substitution Reactions 7. Heterocycles Copper-Lithium Reagents and Other “Ate” Complexes 8. Lithium-Halogen Exchange Reactions 1:: Reductions and Radical Anions 11. Reactions with Inorganic and Orqanometallic Compounds 12. References 1. 2.

1.

:: 21 31 35 37 43 5% :: 68 78

REYIEWSAND ROOKS Reviews and chapters

lithium

chemistry

in books devoted

included

- 13C XMRof organolithium - Fast reaction

studies

- Use of lithium tron-transfer thesis

process

- Annulation - Syntheses - Preparation

(1977)

or in part

to organo-

[1,2]. in solution

addition

reactions

c31. as models for an elec-

[4]. in the use of organolithium

reagents

in organic

syn-

preparation

and synthetic

uses of

ketone enolates

[6]_

[7]. of caretenoids of alkenes

[8,9]. from tosylhydrazones

Annual Survey covering l-131_

wholly

[S].

- Regiospecific

Lithium.

reagents

of carbanions

organocuprate

- Recent developments

either

the following:

the year

[lo].

1975 see J.Organometal.Chem.,

130’

2

Recent methods forthe

synthesis

of polyfluoroaromatic

Preparation

and chemistry

of unsaturated

Nucleophilic

substitutions

at acetylenic

- effects

Allopolarization tiona?

anions

carbon

of substituents

acylation

[13].

on the reactions

reagents

Metal-ammonia reduction compounds [18].

and related

reactions

solvents

in organic

synthesis

Boranes and heteroboranes

[23]_

Metalloborane

with ligand-metal

derivatives

metals

plexes

in organic

synthesis

single

bonds [24].

[25].

nucleophilic

aromatic

substitution

metals

[26].

in :-arene-metal

com-

[28].

Transition

metal dialkylamides

- Gold chemistry

organometallics

metal derivatives

- Preparation

and disilylamides

[29,30].

[31]_

- o-Bonded actinide - Alkali

carbonyl

[19,20,21,22].

c-Alkyl and -aryl complexes of group 4-7 transition Metal-carbene complexes in organic synthesis [27]. Metal assisted

[17].

of =,%unsaturated

_

complexes

Transition

of ambifunc-

[15].

utility of P-oxazolines [16]. of alkali metals in ammonia and other

Boron “ate”

compounds [ll].

[12].

[14]-

Nucleophilic Synthetic Solutions

lactones

of chiral

of tin

[32.33,34-j. [35].

trioganotin

halides

using

organolithium

reagents

[361- Preparation - Inorganic and other 2_

of new homoleptic five-membered hetero

elements

and amides [37,38].

systems consisting

X-ray diffraction

nitrogen,

[39].

has been employed to determine

of dilithiated

(TMEDA) (Fig_

stilbene

the hydrocarbon

to one another.

The lithium

portion

atoms chelated

above and below the midpoint

bene molecule.

The stilbene

~-delocalized other

carbanion

than disolvated

and crystal

bis(lithium

2) [40].

PMDTA)structure atoms_

rinss

by the amines are located

of the olefinic

complex to be isolated lithium

(PMDTA) (Fig.

is planar with the aromatic

equal distances

contains

the molecular

complexed with tetramethylethylenediamine

1) and with pentamethyldiethylenetriamine

In each structure,

first

of silicon,

STRUCTURE AND BONDINGSTUDIES

structures

trans

alkyls

ring

at

bond of the stilis said

to be the

and so characterized

which

Solution

X-ray scattering

have been used to determine diethyl

ether

distance

solution

is estimated

most probably

as structure

the authors

of 1 with methyl iodide, and accounts

reactions.

paper,

In another

in dimethyl

for

its

I Li

I Li

I

I

I

that

LiCu2(CH3)3 (2),

ether of LiCu(CH3)2,

I Li

the dimeric

struc-

in Corey-Posner to show the ore-

and Li2Cu(CH3)3

(3)

[42].

3

CH3-Cu-CH3-Cu-CH3

CH3-CL.-CH3

A la;-ge number of other study organolithium

publications

First,

reagents.

of R- and racemic

structure

The copper-copper

unusual reactivity

I_

fine

1 [41]-

and ‘H h?tR as a dimer in

‘H NMRhas been employed at -136”

CH3-Cu-CH3-Cu-CH3

spectra

exists

conclude

CH3-Cu-CH3

i’

depression,

dimethylcuprate

fi and the methyl groups are either equivalent Based on kinetic studies on the exchange even at -60”.

ture of 1 is important sence

vapor pressure

to 4.420.7

or undergo very rapid reaction

methods, that lithium

also

line

shape analysis

2-methylbutyllithium

as a result

of chemical

described

shifts

‘H !iHR to

the use of

in 300 FTHz‘H NFlR

hexamers in pentane has revealed among diastereomeric

aggregates

The spectra of the racemic reagent indicated 1) an inversion at carbon c433. bonded to lithium which occurs within a hexamer aggregate and 2) an interaggregational

exchange

of organolithiuas

In constrast,

the R-lithium

the inversion

process.

processes

reagent

showed a line

The heats and entropies

inequivalent

sites.

shape chanqe ascribed

of activation

for

only

to

the two

are listed.

The unstable by metalation as evidenced

lithio-Z,E-1,3-diphenylallyl

by XMRspectroscopy

and the following tl,2(-30°)

values

on its

are recorded:

The later

in similar

(4-Z,E)

and by reduction

of

perdeuteratedphenyl

of 4-Z,E to the more stable

= 2-g min. 4-Z,E

anion

of cis-1.3-diphenylpropene

rate of isomerization

observe

between magnetically

5 by lithium derivative.

4-E,E was followed

tit* = 17.321.8

value explains

has been obtained

kcal/mol.

why previous

The by RR.9

~55. = 2.028

workers

failed

studies.

r

Li+

7

bh

. I!3

4-Z-E

A ;

H\&+/Ph

H

Ph

Ph

H

5

metal

4-E,E

e-u.,

to

Several studied

9-aryi

by both

magnitude of ring bered ring tuents

[45].

9ave linear

nhich

ho;;roaronatic

based on SIR alone

Metalation annulenyl

theory

conclud?

that a ring

that paratrclisn magnetic

results

dipo?e

that one might conclude compound [46]_

without

a caveat also

Since

is issued

considering

cur-

of the ‘:.M-LUYO energy oao. frop

low-l:/ing

transitions.

a suffi-

that 7 is a completely

earlier against

stabili:ies

work had demonstrated reaching relative

such conclusions to an aopro-

compound_

7 of hydrocarbon systei

data _ This anion ion e;:hibiting

of the eight-men-

P

the authors

is a function

8 9 by c-butyllithiun

11, whose ‘H iMR was compared to that of [13]

shifts

(6) were

groups on the

of the ‘i! WR spectrum of 7 with that of 9 reveals

number of similarities

reference

the chemical

through allowed

that 7 is not homoaromatic, priate

styrenes,

the current

accessible

A comparison delocal iced,

Since

anions

of such aryl

with the tr values of the phenyl substiP the trend of >max values relative to ? !r opposite to that

support

states

the effect

plots

is being observed

These results

cient

of methylenecyclooctatrienyl

with para-substituted

rent effect excited

currents

protons

and since

observed

derivatives

‘H M+iRand UV to test

cs7j.

12, a peripheral

It is concluded

is apparently

anti-aromatic

the first

properties.

has given an anion.

that

structure

perturbed 10 best

example of a perturbed

10 or

arorr.a:ic fits

annulenyl

the

an-

n-butyllithium

A novel

by ‘H NMRto involve spectra

were obtained

rearrangement

of 13 to 14 has been shown

the intermediacy

of carbanions

15 and 16 [48].

for

The latter

of 17 to 18. preparation

catalyzed

the corresponding represents

intermediates

a new and very convenient

of the 4,8-dihydrodibenzo[cd,gh]pentalene

sulfur-containing

10-a electron

for

the

15

18

17

16 Two cyclic

route

system.

14

13

Similar

in the conversion

anionic

systems have been studied

In the first

case,

19 gave 20, the ‘H NMRof which led the authors

to speculate

the presence

planar,

Secondly,

by NMRto determine

the extent

10 n-aromatic

delocalized

ture of 2i and 22 afforded is delocalized

into

of aromaticity. system [49].

23 whose ‘H and 13C HMRsuggest

the thiophene

ring of this

/\ 0 f3+3-CH3

molecule

0 -

of a mix-

that negative

charge

Li*

20

(WLH3)- Li+

a,,, 22

23

of

of a

[50].

0

19

21

metalation

metalation

i Evidence data for ides

has now been provided

the previously

(24)

and alkali

inferred

dipivaloylmethides

vided data as a function ample,

the greatest

lithium

cation

cation.

In

E.Z-

(26)

kali

cation

by ‘H NMR, far

ion-pair

[52,53]_

alkali

is lithium

sities

of the signals

cator”

in the titration

solvent.

and the E,Z-isomer from

shift

of the cation. was produced

was effected

pro-

For exby the

by the cesium

in methanol as a function

acetylacetonates

In this

cation

dibenzoylmeth-

Each of the techniques

‘H XHR has been employed to study the amounts of

papers,

(27)

[51]_

charge density

downfield

and conductance

of alkali

in the ‘H RNR spectra

shift

the smallest

tWo other

and Z.Z-

(25)

of the positive

downfield

while

infrared,

structures

both

chelation (26)

is unimportant

predominates.

conformations

have

of sodioacetylacetone

except

cji al-

when the

The integrated

inten-

been employed as an “indi-

with lithium

salts

H

H

H

24, R = Ph

26

27

[53].

25, R = I-C4Hg_ Radical

intermediates

dichloromethanes

(aryl

by ‘II and “F

studied

Such effects arylmethyl

in the reactions

chemically

were observed and butyl

of diarylchloromethanes

= phenyl and pentafiuorophenyl) induced

nuclear

on 28 and 29 arising

radicals

polarization from in-cage

and recombinations

and aryl-

with n-butyllithiun effects

were

[54]_

recombination

of arylmethyl

radicals.

of re-

spectively.

,!r(Cl)

tively

example of diastereotopic

charged

silyllithium

silicon

[55].

the nonequivalence of 185”_

A barrier

Metalation ‘H,

atom has been observed

of the diastereotopic

nega-

in the case of diisopropylphenylof this

comoound revealed

methyl groups even up to temperatures

about silicon

of two phosphonate

13C, and 31 P NMRspectroscopy

metalating I-butoxide

groups caused by a tricoordinate

Thus, the ‘H 270 MHz NMR spectra to inversion

I

Ar(C1) 29

28 The first

CHAr

ArCH-

AriHC4Hq Ar(C1)

esters to afford

of >24 kcal/mol

is suggested.

(30,

R = H or CH3) has been shown by eithe. r 31 or 32 depending upon the

Thus, while E-butyllithium affords only 31, lithiumagent [56]. and potassium t-butoxide gives both 31 and 32; the latter species

S

predominates

with potassium

cation_

CH3CH20,

CH3CH20 \ , CH3CH20

[

CH3CH2dp%-+C\.OCH 0

5-

CH3C”20’r2CH3 O-_iiO*

3

6

R 31

30

1

Finally,

H NMR, infrared,

33 and corresponding and the related tion

CH3CH20,

:I

q--iHC02CH3

sulfur

arsenic

of silylethers,

32

and Raman data have been published

and selenium

derivatives

phosphines,

derivatives,

and for

These species

[57].

for

lithium

alkoxide salt

were prepared

34

by reac-

and arsines.

H3SiOLi 34

33

tra of

were its

obtained

dianion

from

tetraphenylethytene Lipfield

[58].

Tines for

of the dianion

both the dilithio

ions are also

of alkali

of the metal,

and the cation

size,

the hv-

than is the latter

one.

gave

as only one other

midway

are rapidly

Ultraviolet

spectra

exchanged of the dian-

The authors

[SS].

between the contact

the

u-carbon

of the enolates

alkali

metal salts

of several

and others

chemical

with

enol

compared to the reference

density

at the a-carbon

shift

where shield-

of the ion pairs

[60]_

derived

and the

same carbon

ethers

shifts

as the

to be spread more evenly

the chemical

metal enolates the

the exis-

chemical

shifts

of lithium

is emphasized_

have been obtained

compared

and trimethylsilyl

charge

The danger of comparing

n-system.

atoms

the negative

discuss

ion alpha-carbon

dependency on these

causing

by ’ 3C NMRas a func-

has been studied

and temperature

the solvent

The 13C NMRspectra

r-electron

as well

salts

t%e lithium

and sodium cations

that cations

reactions.

diphenylmethanes

dependence

to those of other

acetates

is suggestive

solvent,

is decreased

cyclohexanones, late

both lithium salts

ppm for

compound confirms

in the order methyl-THFz-THFXiME, and solvation

temperature throughout

and disodio

ppm and 43.42

to the dianion

containing

and intramolecular

tence of a linear

salts

dilithio

such spec-

Thus,

reported.

Solvation

ing occurs

52.66

is closer

and disodio

betr-reen the above two lines by both inter-

and the

of

compared to the parent

that the former cation

That solutions

tion

shifts

respectively,

and sodium salts, pothesis

to ’ 3C IiMRof organ01 ithiums.

papers were devoted

Several

from acetophenone,

chemical

atoms

of

The difference

the

shift

of

in chemical

compounds seems to be related

and is a function

of

the

corresponding

the cation

enoenol

shift to the

(K*>Na+>Li+),

9

the

solvent

(DME>THF>etherf,

and added

Tigands

Tike

HYPA and certain

crown

ethers. A l3 C WR port

the

of

several

coupling

were found to be higher ascribed

coupling

-t-lithiosulfoxides

such carbanions

that

Thus, the 1J(13C-H)

[611fones sult

study

theory

is in the opposite

pounds methyllithium

and cethane

reagent

in radicals

butene

is discussed

not be understood radical

of

18-crown-6 ducts

ether

The authors

adequately

without

ketyl

of

thienyl

[65],

were also

sui-

with the model com-

constant

is

smaller

in the

1,3-carbon-carbon

interactions

cyclobutene,

that “spin

conclude

recognition

of

is not necessarily

these

on spin

and trans-2-

densities

simply can That

interactions.” than such anion

greater

soio

is discussed_ for

phenalene

35 [53],

phenyiazulene

2.2,6,6-tetrarzethy’cyclohexanone and thiazoyl

five

of phenylacetylene

troscopy

of

[62].

have been reported

various

and

sulfur compounds, a reThis increase in the

realized

the coupling

SUD-

position

lithiosulfoxides

state.

direction

uhere

the

in the parent

from benzocyclobutenes.

to 8-hydrogens

the lithium

ketyls

derived

hyperconjugation

ESR spectra [63],

of

does not

even in a benzylic

than in the hydrocarbon.

In the area of ESR, the effect density

:ransmissions

constants

than those

to a change in the hybridization

constant

organolithium

cation

and sulfones

are pyramidal

ketones

arylphospine

1673.

including

derivatives

In the latter

employed to demonstrate

[6a].

and alkali

infrared

36 rwtal

of dihenzo-

the affect

f66],

case,

alkali

metal ad-

and optical

spec-

the reduced nature of such species.

4 0

36

35 Spectroscopic

studies

to be investigated. rivatives

of

Thus.

nitromethane

using the

techniques

infrared

other

in the C-H stretching -1 are ascribed

m31- Bands at 3040 and 3170 an

with a sp2 hybridized carbon atom. The infrared spectra of several bonylates

were obtained

ment [69].

The data.

provided contact

information and solvent

to indicate in connection

than ::MR and ESR continue

and Raman spectra

alkali

region

of

alkali

metal derivatives

formulation of manganese caranion environ-

and conductivity

experiments,

about the nature of bonding and complexation separated

ion pairs

as well

as in

de-

have been investigated

to the aci-nitro

the nature of the carbonyl with kinetic

metal

free

ions

phenomena in of

several

10

study.* resolution

species.

In an unrelated

rections

of the transition

obtained

by the use of absorption

Ultraviolet

spectroscopy

brium constants lenide, anions

causing

by.the

an increase

The ion pair

and the di-

at 860-560

have been

nm [70].

and ESR have been employed to measure the equili-

tetracenide,

are favored

structure

lithiotetracyanoquinidometiiane

spectroscopy

of the disproportionation

anthracenide,

reactions

moments of

of vibronic

of the ion pairs

perylenide.

interaction

of

the cations

in the coulombic

propagation

with the aid of UV spectroscopy

actions

[72]_

Three types of anionic

Iithium

in ether

naphtha[71]_

The

with the resultinn

di-

energy.

in the polymerization

studied

of

and pyrenide

of

to check for centers

isoprene

in THF has been

the occurrence

are observed

of side-re-

at 287 MI, 305 nm,

and 335 run. two of which may be due to 37 and 38. Li+ -CH2-CH\~-+CR2 ZH3 38

37 in this

Other papers of interest arylthiolate

anions

the ion pairing (ethylene

using

alkali

visible

1751, and determination desorption

studied

mass spectrometry

with methyllithium values

l-727,

2.025;

C-H bond length

1.078.

1.0623

to 1.1185

(if said

tetrahedral

mostly

from the lithium bond is suggested

-46.9596, -46.4203.

calculated

to be -185.4886

to -185.8611

total -53.744

energies [78],

(8):

-39.318

The total

described

papers were employed,

2_021:1_q69. 104.2”;

to -39.401,

(Hb), total -46.419

Monomeric methyllithium

[79]. (&:

hartrees

of the C-Li barrier

[Sl].

species

Clusters

ranges

tetramer

Li-Li:2.369-2.68;

energy of this

is

transferred

Methyllithium

Li-Cr has been

containing

[Sl].

of methylenedilithium

-53.131

by

[76]_

(Ha) and 1.068 105A”,

and the inversion

as follows

[Sl].

spectra

sets

The bond separationenergy

upon bond angles

as having bond lengths

Similarly,

five

bonding with about 0.8 electrons [78]

[73],

of carbanions

attachment

1.090

of

of poly-

substances

reagents,

1.122,

planar),

kcal/mol

are also

cation

C-Li bond length

l-089,

C-H: 0.95-1.095

be (hartrees)

lithium

upon angle);&H:

2.25-2.31;

ten atoms of lithium

formation

Depending upon the basis

to the methyl [77]_ to be -5.6

spectroscopy

of non-volatile

-46.7767,

of ionic

ion pairing

and fluorescence

on organolithium

(ii):

(if

from O-4 to 20.31 depending is described

using

(depending

) , -46.247

to consist

weights

have been described:

energy (har Zrees) : -47.0206,

ion pair

[74].

[77-al].

the following

by optical

by absorption

of molecular

In the area of calculations concerned

a study of

metal compounds in the presence

spectra

of xanthene and thioxanthene field

include

in THF and DMFdetermined

of fluorenyl

oxide)

area

(cis,tetrahedral)

have been calculated [80],

-53.074

to

to -53.030

11 (trans.

planar)

[SO].

wise described 1.208 i;

C-H bond length:

charge distribution calculations, state

and -53-7165

by the following:

1.056 w [77].

in this

of 39 rather

are discussed

[SZ].

Lithioacetylene

Another paper discusses

than 40 [84].

including

A wide variety

I-fiuoro-i-lithiocyclopropane,

42. and others

Li C

C--

Li-CsC-Li

40

Using ST0/3S atomic (43)

of solvent

lithium

A calculated E86].

time scale, = solvent cussed. suggested C871-

computations

structures

l-l-di-

below [S’i].

H

soecies,

computations

of pentadienyllithium

a bridged

lithium

CT and C5 have previously structure

dimethyl In another that

were performed

on both the co-

[SS].

In an attempt were also

it is concluded to determine

oerformed

the

on all:Jl-

to two trater noiecules.

structure

this

42

of allyl!ithium

than 43 by 6 kcaI/moI.

which contains

Since

(44)

on this

coordinated

proposed

41 and its described

41

orbitals,

and ion pair

that 44 is more stable affect

ethyl-

1-3-dilithiooro-

H Li

39

valent

orqano-

[77],

6, + 1; --;---(

Li

usino ground

of other

and vinyllitilium

and LiCH2X where X = LSeH, XH2, OH, F, and 9H2 1781, pane, difluorodilithiomethane. tri- and tetralithiomethane. salt,

the electronic

bridged

lithium

lithio

like-

paper or-edicts,

has a’double

ethyllithium

is

1.931 .t; C-C bond length:

compound 1833 Nhile a third

that monomeric dilithioacetylene

structure

lithiums

to -53_7851

C-Li bond length:

ether.

is said

the lithium

interacting

ether)

by both :-

has been

and z- bonds

been shown to be equivalent

to be equilibrating

The affect

paper dealing

bis(dimethy1

on the F!YR

as shown (45)

where 5

of methyl groups on such anions

with cyclopentadien:rllithium,

atom is most stable

it

is dis-

has been

above the middle of-Ehe

rino

12

Other ring [80.88],

clopropenyl tion

systems similarly

anions

[go],

anions

aromatic

and antiaromatic

dianions

[88].

Two papers discussed Both agree

the orbital

containing

stable

have included cyclopropane

4-,

‘;-,

certain

b-,

7-,

of 3-oxypair

atom rather

[91],

[89],

reac-

anions

and 1-thiocarbanions

are stabilized

[92.

bonding.

Such sta-

is conformationally

than conformer

dependent where conformer 46 ( w or e) is more are oroSimilar nc-siH overlap integrals 47 (y or a)_ It is suggested

the C-H bond antiperiplanar

to the lone pair of electrons

is much less

acidic

than that

in its

H. “<-.

that

precursors.

on the -:t-heteroaton,

H H

/

C

in such carbanion

gauche rotarner.

H

d_.

Q Y X

‘.

\‘C

;

B

46

\

47

ii

An -ab initio study has been performed on nitromethane. its aci-nitro and its conjugate base 49 [94]. The anion is best described

tomer [48],

but has an extremely

The total parent:

and

by overlap of and a .G* anti-

of the carbanion

than by (d - p),

posed for e-oxycarbanions_

planar

cy-

and other

and g-membered ring

alpha to sulfur

the lone electron

on the sulfur

anion

the electrocyclic

ant! butadiene

8-,

aspects

lithiocyclopropane

radical

[80],

of cyclobutene

that carbanions

bonding orbital bilization

[80],

3,3-dilithiocyclopropene

between the radical

931.

studied

I-l-dilithiocyclopropane

energies -243.2630;

CH2=rI

shallow

(hartrees)

for

48: -243.2532;

potential

49:

to pyramidal

using an extended

inversion_

basis

set are

-242.6573. 0

r”

-

H.$..

\ OH

+// \

o-

H#=N

a 0-

48

+i’ I

0

_

49

Other Papers discussing

mdlecular

with the SRy 1 mechanism of aromatic anomethide’C961,

curve

the species

tauas

and the structure

orbital

calculations

substitution

of the lithium

[95],

have been concerned

the structure

of tricy-

adduct of nethylenephospho-

rane [97]_ 3_

KINETICS AMI MECHANISM Several

to test cesses

if

:ypeS of ketones have been condensed with lithium dimethylcuprate the nature of the products could determine if electron transfer pro-

had occurred

to afford

radical

anion

intermediates

C98.991.

Thus, aryl

13

alkyl

ketones

tions.

50 with this

Though ketyls

detected_

Similar

attack

than to an electron was observed of

cuprate

products

transfer

process.

no products

ketyls

arising

from 51 were

of certain

ketones

52 gave

on the cyclopropyl

On t.he other

ketone 57.

diary1

ring

transfer

54 to ketone 55 and

In another

ketones

were rather

hand, such electron

and bromoketones

enone 56 to E.-f-unsaturated

affords

from 1.2-addi-

53; horrever, such products

reagent

of acetoxy-

that the reaction

arising

with cyclopropyl like

by the copper

in the conversion

Z-cyclopropyl

is disclosed

of the cuprate

ring-opened

to direct

gave methyl carbinols

may have been present,

reaction

some of the desired ascribed

cuprate

paper.

with lithium

it

dirrethvl-

[loo].

0

R’

53

52

51

50

R

0

R

0

0-

I

54 The electron been studied [lOi]_

transfer

as a function

efficiency

of g-methoxyfluorenide

in methanol has

of the nature and concentration

It was found that the second-order

irreversible

57

56

55

nitrobenzene-oxygen

trapping

rate

of

constanis

efficiency

the counterions

for

ionization

are in the order

and for (CH314N*

~l~~Y,OCH3~~ilaOCil3--LiOC~3_ Benzhydryl by lithium

results

These

chlorides radical rate

are conirasted

to similar Similar

in the reactions

mass spectrometer

and absolute

gas phase acidities

Such acidities

transfer

reactions

mechanism [102]_

of corresponding

mechanism through a geminate

mechanisms are suggested of diphenylmethyllithium

is of

is discussed.

rates

of a variety by pulsed

The relative

of several

since

to explain

the

with benzylic

of

anions

resonance

acids

[103]. of sol-

the measurement of oroton-

with related

spectroscopy

58 and 59 towards

why desired

electron relative

and the importance

Another paper describes

to determine

in a pulsed it discloses

carbon and nitrogen

acidities,

of delocalized

ion cyclotron

reactivities

in an effort

generated

interest

are compared to solution

energies

as determined studied

coupling

gas phase carbanions

hioh-pressure

transfer

to ethane derivatives

displacement

and chlorides.

A paper describing

vation

have been dimerized by a classical

via an electron

intermediate_

differences

fluorides

apparently

which occur pair

fluorides

and benzyl

naphthslene

alkyl

neutral

halides

ranoalkylations

species

[104]. have been

of species

like

14 58 afford

of mono- and dialkylated

mixtures

that such carbene

anions

of the more substituted

suffer

products

dialkylation

The authors

[1051. of

because

the greater

conclude

reactivity

anion.

58, R = H 59. R = CH3 The equilibrium lithium

anionic

polymerization

of n_-valeraldehyde

benzophenone has been investigated

of -5.3-0.3

kcal/mole

and -25.7r1.4

cal/mol-deg,

effected

by

Enthalpy and entropy

[106].

respectively,

values

have been dis-

closed. Equilibrium ters

solution

acidities

of a number of phosphinylacetic

in diglyme and in DMSOhave been disclosed

it has now been established are observed tions

that kinetic

not only with different

The kinetics

of the disproportionation

of the alkali

illustrates dianion

cation

salts

by fluorene solvents protonated

ion pair

is protonated tight

tTll]_

tetracenide

four-five

The kinetics

alkali

ca-

The study

radical

anions.

orders

of

species

faster

than the cor-

fluorenyllithium

the former system reacted

and solvent

has been

separated two-three

ion times

one_ of alkali

derivatives

of the cation,

to the tightness

with the potassium

of ethyl

the solvent,

of ion pairs

[112-J.

than with the lithium

of the solvents

acetoace-

and the alkyThus, more salt

and in

are deemed more important

than

constants_

Other kinetic

studies

and lithium and styrene

have been performed [113],

n=butyllithium

on the systems bromobenzene, and 4-methylmercaptoaceto-

and lithiumdiethylamide[115].

in the area of stereochemistry,

the Z/E equilibrium

is

and that the sodium

of magnitude stuay.

of ethereal

the lithium

ion pair.

carbanions

and sodium

in a variety

ion oair

an-

for certain

1,3-diphenylallyllithiun

revealed

RWA than DMF- The ionicities

phenone [114],

corresponding

of

In another

of 0- to C-alkylation

dielectric

radical

as a func-

[109].

free

than the latter

is realized

photolysis

favoring

agent and is ascribed

benzaldehyde,

flash

than the tight

has been found to be a function

0-alkylation their

of alkali

spectrophotometrically

ion pair.

under conditions

The ratio lating

Hith different

it was found that the loose

lithium

more rapidly tate

but also

ones may be responsible

than their

the protonation

about 100 times faster

responding pairs

of C-H acids

have been determined

using

than steric

have been determined

[llO]_

alkylated

other

being more stable for

dianion

and solvent

that factors

Rate constants

tight

effects

espaper.

[lOS]_

ions to the parent compound and its tion

differentiating

anions

acid

In an unrelated

[107].

compositions

of

15 several

E-alkenyl

been studied the Z/E ratio endo (cis)

organometallics

as a function increased

preference

60 (R = CH3. CH3CH2, i-C3H7. f-C4H9)

of cation,

in the order

R, and solvent

[116]_

Li
between R and the alkalimethyl

pendent on the electronic

capacity

or the size

carbon

of R.

have

It was found that Moreover,

the

seemed not very de-

Reasons are suggested

for

the above observations. RCH = CHCH2M 60 3-#ethyl-Z-pentenyllithium hydes , acetophenone,

mounts of branched factors

[117]_

p-electron

has been condensed

acetone, (61)

and linear

The ratio

withdrawing

alcohols

of 61/62

groups_

ing groups _ Only 61 and only The results

respectively.

with a variety

and hesafluoroacetone (62)

decreases

a-

electronic

with o-electron

VJith acetone

in terns

of

of benzaldehydes

is realized

62 are obtained

are interpreted

as a function

in reactions

The opposite

of benzalde-

to study the relative

with donat-

and hexafluoroacetone.

of hard-soft

acid-base

theorv. OH

OH

/+AR

-_-

-_.. >

i 62

61 The effect

of

has been studied higher cifically

alkali

metals

with methyl

gave nearly alized

ion pair [llS]. iodide

a SO-50 mixture

in terms of a cation

63

siructures

in THF by varying

on the methylation

the cation

Thus, while to afford of mesoside

the lithium

meso-

of nethyl

64

salt

(:- 99:),

and racenic-64.

approach

stereochemistry

systematically

from lithium 63 reacted

iodide

63

are ration-

to diastereomer

65

to the

stereosae-

the rubidium salt The results

of 63

65.

16

i4etalation

to afford

of

(+)-(S)-3-methyl-Z-pentanone

(S)-enolate

has been reacted give optically

67 with less

with alkylhalides. active

hy LI\IP&has been show

(66)

than 10% racemization acid

chlorides,

Reagent 67 and ketones

to

products _

0

Oti

67

66 In the continuation of addition

[119].

aldehydes,

reactions

of an earlier to carbonyls

study concerned

with the stereochemistry

in terms of orbital

factors,

the relative

amounts of 68 and 69 from 4-t-butylcyclohexanone with MCH2Y\-rere found to vary Thus, less 69 was obtained with LiCH2Y than with the metallic cation [120]. with BrZnCH2Ywhere Y = C02C2HS. CONR2, CIi. and CO2M.

69

68 Several afford

ester

the 1,2-adducts

terestingly, ing,

lithium

the thermodynamically condensation

have been*condensed

70 at -7g0 by a kinetically

when the reaction

a similar fordino

enolatrs

mixtures

controlled

are allowed 1,4-adducts

with a lithioacetonide

with 2-cyclohexenone

controlled

process

to

[121].

In-

to warm to 25” before quenchIn one case, 71 are obtained.

was found to.be

irreversible

af-

only a 1,2-adduct.

LiO

t;i

+

CH3$Cfl$H3 X

The intermediate lithium

-7 71

(X = CH3.0Ph.OCH3.SPh.SCH3)

70

dimethylcuprate

ium enola:e

organometallic

to enone 72 has been found to consist

73 and insoluble

troscopy

[122].

probably

intermediates

obtained

from the conjugate

(CH3Cu), precipitate

It is suggested in all

even when the organocopper

that

lithium

such conjugate

product

as evidenced

rather additions

remains in solution.

X C02CH3 addition

of

of soluble lithby 13C RMRspec-

than copper of lithium

enolates cuprates

are

li

OLi

0 ether

(CH3)2CuLi

73 Other sutudies (S)-lithiobenzyl acid

[123],

in this

the stereochemistry

dihydroanthracenes valent

[124],

phosphorus

nethoxide

to afford of

the silylation

and the inversion

atoms of two phosphinate

with the carbonation

of

(R)-:i-nethylsulphinylphenylacetic of 9-alkyl-lo-lithio-9,lo-

of configuration esters

at the chiral

by methyilithium

tri-

and sodium

[125].

Several 1976.

area have been concerned

methyl sulfoxide

papers describing

A continuation

has resulted

in the discovery

control

[126].

erythro

acid

For example, enolates

has also

of organolitiiums

of the ester

enolate

of solvent

that choice lithio-(E)-crotyl

75 in TtiF and to threo acid

Z- and E-type

reaction

rearrangements

of the study

appeared

Claisen

dictates

propanoate

in

rearrangement

stereochemical

(74)

rearranges

to

76 in THF-HHPA. It is suggested

This

are formed in THF and in THF-HHPA, respectively.

been employed in the construction

of the prostanoid

[127]. H

H

that

skeleton

-

CH3

” vCH3

.-

OH ti

of alkali

The isomerization all

for

cis

77

_‘._ _:

and potassium

cations,

been effected

by protons

anion 77 to the

a much higher

where the &Gf of the isomerization

lithium

of 77 to 78 has also

.;

cis,cis,cis.trans-[gjannulene

78 has been found to require

than topomerization kcal/mol

76

74

75

more stable

OHH

0

CH 3

respectively

activation

energv

ranged from 29.6-34.3 Isomerization [128]_

and by photochemical

78

and thermal

16

A fuT1 paper appeared describing

with cholesteryl ring

systems participate

found for result,

Several

ring

salts

the Stevens rearrangement ethyl,

tosvlate.

reactions

were

As a

which occur

sp3- carbon atom_

of methallyamines

have been subjected

to

to 82 and 83, respectively_ %th larger alonly 82 arisinq from 80 was ohserved.

81

80

i

R-R’

R’

83

82

86 [131].

results

and cyclohexyl,

R /J ’

Quaternary salts

Similar

and other bases [130]. When R and the reaction proceeded via a mirand n-butyl.

79

bases to afford

dialkylcuprates

by n-butyllithium

n-propyl,

i-propyl

lithium

[129]:

in these

at the nucleofugal (79)

ture of 80 and 81 which rearranged kyl groups like

reactions

are observed

of configuration

of

in which the double bond of the

of cyclopropylmethylcarbinyl

reorganizations

quaternary

R’ .were methyl,

tosylates

in substitution

the cycTopropane

skeletal

with retention

the interaction

and 5-norbornen-Z-y1

84 (X = Cl,I)

Stevens rearranged

The amines arose

were also product

treated

from a cormnon intermediate

a5

with a variety

85 and Sommelet rearranged

a6

87.

87

of strong product

19

Similar

have been observed

rearrangements

amines 33 and benzyne.

generated

[1323.

Among the products

induced

by excess

in the reactions

from o-fluorobromobenzene

observed

of silyletkyl-

and n-butyllithium

The cyclization

were 89-91.

to give

90 was

n-butyllithion. :*3

Certain sulfones step

like

h-arylbenzenesulfonamides 93 upon treatment

in such reactions

fonyl

like

92 have been found to rearranqe

with organolitkiuo

is metalation

91

90

89

88

of a ring

reagents

[133].

to

The first

hydrogen atom ortko

to the sul-

group.

93

92

The previously

reported

found to be reversible lithium

counter

[134].

rearrangement

stabilities

Na

I

I

Pk C-R 2

N-Ph I

to 94 by tke use of

of sodio-95

c0zc2*5 Ph2‘,

of 94 to 95 has now been

Thus, 95 may be converted

The relative

ion.

discussed.

1,2-anionic

,’ \

versus

lithio-94

are

C02C2H5

-Ph

Li

95

94

Ketazines their

have been converted

Jilithio

is determined

salts

as illustrated

to pyrroles

or tetrahydropyridazines

in Scheme I [135]_

Which nroduct

via is formed

by the nature of the R and Ar groups.

R mechanism has now been proposed for the conversion of 96 to 97 involving, lithioaziridine 98 which has been trapped among other proposed intermediates, with methanol-O-d

[136].

0

0

P

NH-c-C6Hll

I c-C& 96

1

Ph 97

I c-C6Hl 1 98

20

Scheme 1

Ar

I

Products from

the

99-101

tiittig

(R = 5-hexenyl

rearrangement

by n-butyl-

and methyllithium

group

via

arise

of

pathways

secondary recombination of alkyl to 99-101

which

contain

the

orcyclopentylmethyl) benzhydryl

[137].

intramolecu’lar

2.2-3.0 LDIpA THF

radical

Ghexenyl

have ether

in

been obtained THF effected

Those products containing the 5-hexenyl which

may involve

and ketyl.

cyclopentylmethyl

group

routes

other

The cyclizations are

said

to

occur

than leading with

5-

21 hexenyl

radicals

which escape

with appropriate

reaction

with geminate

partners

but later

react

ketyls. R

!

; &

Ph2C-OH

.cFL/

*6&.Ph P”.

_. -’

( Ph 99 Two papers discussed siloxybenzenes. lustrated

and other

pyridines.

by the conversion

some cases,

of

fail

[lSO].

a portion

the synthesis

rides

4.

of

substitutioh

in contrast,

il-

route

in

1 ithio-‘J-

of the first

in the reactions

have been concerned

with the con-

rearrangement cyclophane

of a dithiacyclophane

within

a cyclophane

as

[ICl],

and

of tributylstannyllithiun

with aromatic

fluo-

have been metalated

by n-butyllithium/T!-?EDA

c142].

METALATIOZS A.

At so3 Carbon Several

polymethylbenzenes

in hexane to afford tion

The process,

to (El-2,2-diphenyl-l-methylthiovinyl-

the us;? of the Vittig

and chlorides

in others.

rearrangements

of 5,5-diphenyl-4-thiacyclohexene

cyclopropane tine

route

[139,139]_

by an intramolecular

to undergo such rearrangenents-

Other papers discussing version

heterocyclics

102 to 103, occurs

but by an intermolecular

iriaiky1silylarylaaines

101 in lithio-O-trialkyl-

100 anioni c 0 to C rearrangements

[143].

clusively

di- , and trilfthio

mono-,

For example.

mesitylene

The energies

105.

and are included

derivatives

gave mostly

of these and related

104 while species

as evidenced p-xylene

by silyla-

yielded

ex-

have been calculated

in the paper. CHLi2

CtQLi

2Li+ LiH2C fiCH.$_i

@ CH3

104

105

106

33

Four methallybenzenes above reagent

to afford

and isobutene

corresponding That dilithio

by methyl bromide [144]_ :!HR spectroscopy.

The methylated

enes were obtained

in preference

discuss

at great

methane dianion Metalation lithium

the

species

at a benzylic formally

carbon

delocalized

was confirmed

from cross

from linear

of the aromaticity

by dimetalation

of

by the

which were methylated

were present arising

to those arising

question

obtained

metalated

derivatives

derivatives

of 1.2-dihydropyrazines

occurs

tem containing yields

length (106)

have been similarly

dilithio

conjugated

ones.

by di-

The authors

of the trimethylene-

isobutene.

107 (R = Ph or p-ClC6HS) with n-butylto give

bicyclic

Sn-electrons

108 rather

[14S]_

than 109, a sys-

Hydrolysis

of

108 then

110.

108

107 A combination

of metalation-metal

lithium-potassium ene(lll)

t-pentoxide

to dianion

112, a very stable

ple cycloheptatriene cloheptatrienyl

hydride

[146].

elimination

reactions

has been emp!oyed to convert species

Oeuteration

of

by n-hutvl-

l-methylcyclohept-?-

which does not behave as a sin-

112 affords

the known methylenecv-

anion 113.

111 !*letalation

of

112

squalene

113

by s-butyllithium/TMEOA

has been found to occur

only

on a methyl group [147]_ prenylamine

In another paper. metalation of a methyl qroup of 114 by n-butyllithium results in an interesting isorrerization and

elimination

to give

isoprene

[148].

Other related

examples are listed.

114 Polymetalation tion yield

of acetylenes

continued

of 1- and E-butyne and 3-methylbutyne CH3C3Li3 and (CH3)2C3Li2,

densed with a variety

respectively

of electrophiles

to be studied

in 1976.

with alkyllithiums [149].

to usually

Thus, reac-

has been shown to

Such species have been conafford polysubstituted acety-

23

lenes of

and allenes

like

are best

described

sequential

soft

scribes

of

[lSOj_

The results

and acetylide

A second paper in this

are ascribed

sites

allenynes

C3Li4 gives

mostly

to proparqylic

sites

and reactions

and diethyl

C-CCC-Si(CH

)

(f!J3)p

(CSIj3

120-122

lithi?;n

C2%\ .=C=c~C2ii5 /‘Si(Ck!3)3

Zhile

[152j.

r20 and 122 were netalated

to afford

The authors

suggest

by n-butyliithiun

which have been condensed

121 gave a mixture

respectively.

by n-buty’llithium

have been mecalated

reagents

120 Regioselective dimetalations (123)

124 after

122 with chloroirimethylsi-

,Si(CH313

(CH3)3Si ‘C=C=C / &J ) .. ‘2 4

(CH2.i4

CH2-C-C

/

124

123 Seven I-arylpropynes order

rea-

on 1,Scyclotetradecadiyne

quenching

i CH2CXCH2

and trilithiated

of

only at the methyl and

that both netarations occur .ztthe same car-

CH2CXCH2 ‘.\ / (c\H2)3 (CH2)3

Pseudo-first

to

with a variety

of .I- and -:‘-nonolithium

121 have been e ffected

bon atom.

di-,

of which gives

113

proparqylic

lane El53].

being

paper de-

117

33

Cyciopropylacetylenes

carbon,

sulfate

A third

(C,E,),C-XX--Si(C1!3)3

L

118

electrophiles

and chloro-

[llj].

AE

Si

i-ring

hard.

116

2 5’2,

discussed

sulfate

of CH3C5Li3, derivatization

(CH3:2C=C=C,r

115

yield

series

species

117 alonq with some 118

being

and some cumulenes and diacetylenes

i

containing

by diethyl

and chlorotrimethylsilane

!CH3)2;4:c-E

(C 2.1

of which depends upon the size

the above lithium

these organometallics

For example,

the preparation

mostly

ratio

the

as proparqylides.

derivatization

trinethylsilarie and 119.

115 and 116,

An IR study suggests

the electrophile.

containing

various

ring

substituents

on the methyl group as evidenced rate constants

for

have been mono-,

by silylation

the monometalations

[154j.

were calculated-

24

Several

methyl ketones

have been regiospecifically

methyl carbon atoms with aldehydes 126

rl55-j.

by bulky

The success

bases

like

127 in the presence

enolates

that o-methyl-hydroqens

in preference

to p-methyl-hydrogens,

fects.

An additional

-c-hydrogen may also

of an acetylene

lithium

in hexane to give

ionized

via eliminaiion

probably be abstracted

of lithium

trilithio

too weakly

and o-hydroqens leading

ef-

to the foma-

salts

the conversion

131 by LDIPA in THF [158].

using alkali

metal

amides

failed

of triketones

Previous because

attempts these

like

130

to pre-

reagents

are

basic.

A similar

lithium

cyclohexyisopropylamide,

was found necessary

to

of 132 [159].

Lithium enolates fragment as indicated Glycidic

methoxymethyl

132

131

base,

ionization

134 [160].

are

of chelation

129

131)

effect

128

,CH2Li

paper has appeared describing

pare such trianions

like

oxide.

128 to their

SiZ

have been

species

because

,CH3

A full

[156]. .x \ Si

127

by n-butyllithium/TKDA It was established

and 129 [157].

Similar

co-reagent.

from esters

0

ring mono- and trimethylacetophenone

metalated

of 125 to

the metalations

126

125

tion

the aldehyde

OH

Several

td effecting

E-hydroxyesters

n

further

of

on their

by the conversion

of the method is ascribed

have been employed to prepare

bases

as illustrated

condensed

esters.

from methoxyirethyl

esters

at 25” and recombine esters

may be prepared

like

to afford similarly

133, though stable

at -79”.

hydracrylic

like

esters

by metalation

of s-bromo-

Lit

0 /CH20r-i II -- R2C=C=Of H-C-H + LiOCH3 - R2C

3: R2C_E&CH2&-CH3

\

+LiOCH3

133 Lithio-t-butyl talation

of

dehydes

to give

pared simi?arly, [162].

silylester

acceotors.

reacts

(135)

esters

[161]_

Lithio-t-Duty7

with aldehydes

have been (1361,

-:,:-unsaturated

prees-

-_si __-’

ester

enolates

of undergoir;g are

generated

like

thio

by LDIPA at

as Part of

I! R’CHpt 139

to be metalated

organolithiums

to afford

have been

0

138

the resulting

ester

(1381

139 [163].

[164].

As fLi continue

like

with formaldehyde

0

esters

and ketones

esters

the parent

been condensed

137 thio

[166].

of

thiol

of u-methylerie-y-thiobutyrolacione

i CH2=CSR

For example,

to afford

by metalation

OLi

Certain

137 and ,-thiolbutyrolactone

al kylation

136 has also

Lichiolactone

the preparation

alpha

io sulfur

by LDIPA.

140 and 141 have been condensed with

a,?-unsaturated

esters

[165]

and chiral

thi-

respectively.

S(O)

S I!

Li

LiCH2-SX-OR

RO:, , CHC02C2.H5 S

141

140 A variety of

al-

ii

thio

The enolates

tions

of

tl

Lithium

metalated

by me-

a variety

esters

to yield

Li

found capable

iranes

The latter

and ketones

!

aldehydes

with

trimethylsilylacetate

(ESi)2

-73”.

-

has been obtained

by LDIPA and condensed

vinyl

a-silylated

shown to be Michael ters

134

bis(trimethylsilyl)acetate

the parent

co2cc;3

of phosphate

by n-butyllithium 143 with aldehydes

esters to give yields

0

I! _

R2C=;-CH20P(OC2H5)2 R

142

and phosphoramides intermediates

like

like

142 have been di-

143 [167]_

lactones.

.+ 0

‘I’

R2C-7Tq

II (OC2H5) 2

R 0-Lf+ 143

Condensa-

Interaction of N,IJ-dimethylbenzamidewith LiTMP to afford 144 proceeds via The latter organolithium reagent may arise the dipole stabilized 145 [168]. from metalation

of the methyl group syn to the carbonyl a related carbanions are described,

oxygen. reaction

examples of similar ethylbenzamide

results

tional

In a different

group_

mide by s-butyllithium more stable

only

in ring metalation ortho to the carboxanide funcof !1,M-dimethylthiopivalapaper, the metalation

to afford

146 is discussed

than 145 is evidenced

with alkyl

halides,

nucleophilic

aldehydes,

by its

ketones,

aninoalkylation_

[169].

That 146 is apparently

sufficient-life-tine to be condensed Such condensations represent and OHF.

_

146

145 Hippuric

has been converted to its

acid

and then al kylated

to give

similarly

and condensed !_i

prepared 0

148 [1703.

trilithio

Dilithio

salt

salts

with alkyl halides !

YH.I_.

147

Li

of 151 with LOLPA has yielded

yields.

nuder

of alkylating

Similar

as part of the synthesis

i

metalation

/R

;

\-

like

Subsequent

gave d,S-unsaturated

of acrolein

of species

150

152 [172].

agents

OSiZ

OSiE R

Oh

0

of 152 with a large ployed

,/ 0

148

149

in excellent

F

Li

ii lletalation

147 by LDIPA/TMEDA

149 and 150 have been [170,171].

Ph/9

0

Though other on II,N-di-

cyanohydrin

153 11731.

reaction ketones

has been em-

m-Tolunitrile ford

has been metalated

154 [174]_

Condensations

In a different reacted ducts

study,

with various arising

for

the first

with ketones

the three

isomeric

time using LDIPA to af-

and alkyl

halides

are described.

bis(cyanomethyl)benzenes

amounts of methyl1 ithiu ii: and methyl iodide

from multinethylation CR

[175].

155 have been to give

pro-

CIi,CN L

0 a L:

CH2CN

\.

154 papers disclosed

Several with bases

additional

such as LDIFA, lithium/diethylamine

ethylamide.

Such netalated

amines like

kyl halides

[176],

:l-bromoacetals

haloalkenes

[179].

epoxides

imine has also

been cetalated

ot- ii-alkylated

as a function

!177],

dihaloalkanes

and chlorotrinethylsilane

the cation

156

imines

156 and 137 have been alkylated

by netbyllithium of

of

in benzene/RMPA, and lithium

and ketals

[180].

155 of the metalation

exa::ples

to give

[178],

[lSl].

di-

by aldi-

A bis-

158 which has been C-

and solvent

[182].

N

157

Ph 158

In the area of oximes,

the position

Governed by the configuration and condensations

with aldehydes

Thus 159 and 160 afford cyclic

ketones

iodide

occurred

lithio

oximes have also

azoles

[187]

Several after

like

oxines

and their

the axially

[183]

also

work up. hydroxylamines

has been shown to be

and ketones

and by deuteration

[184]_

product

al kylation

[185,186]_

chlorides

to qive

P-isoxazolines

of organolithiums

4-acylisox[ls8]. to afford.

_ Lit R

HO,

160

161

162

by methy

Such di-

163 [189]. Li+

159

alkylation

In the case of oximes from

to yield

underwent addition like

by subsequent

O-methyl ethers,

substituted

been condensed with aroyl

and with aldehydes

lithiated

and ketones

161 and 162. respectively.

cyclohexanone

to give

of -;-netalation

of the oxime as evidenced

163

28

A large

number of N-N-dimethylhydrazones

tones have been regiospecifically

[190,191,192]

ety of electrophiles aldehydes

[191],

to afford

polyfunctional

The use of chiral

chiral

ketones

enolizable.aldehydes

by LDIPA

to give

a;ld ke-

derivatives

[190,193],

v-hydroxycarbonyl.

compounds [192],

165 in alkylation

1,4-

164

with a vari-

aif!-unsaturated

and l,S-dicarbonyl

and a-thiomethyl

reactions

like

species

164 and 165 have been reacted

alkylated

6-hydroxycarbonyl.

compounds, other c1943.

metalated

Reagents

and 165 [193].

of

gave,

after

compounds hydrolysis,

[193].

(CH3)$\ N Li * ,C

‘c

/

iin 165

164 Several

other

phenylhydrazones,

zones have similarly certain All

hydrazones

of these

sis,

tions

168 affords

alkyl

active

halides

ketones

enamines from certain

n-butyllithium

species

to give

trilithio

[199].

chiral

166 [195.196]

reagents

[198]_

sulfate

In a different

indanones

The results

lithioenamine

and dimethyl

like

while

167 [I??].

169 which has been to give,

paper,

and a cyclopentenone

obtained

from subsequent

after

hydroly-

metalation

of pyr-

were effected methylation

by

reac-

are presented.

169

168 Allyloxy lyl

and N-p-tosylhydra-

like

have been condensed with electrophiles. Li

of chiral

by several

optically

rolidine

to dilithio

have been metalated

reagents

Metalation alkyiated

N-benzoylhydrazones.

been converted

ethers

with aldehydes Internal or chloro

carbanions

like

by s-butyllithium and cyclic

cyclization

172, condensations

ketones

reactions

substituents

170 continued [200,201,202].

[201].

to be prepared Condensation

gave mostly a-type

by metalation of

products

of 170 have been observed

of al-

170 (R = Si(CH3)3) like

171 [200]_

when R contains

epoxy

In the case of the related pentadienyl lithium with a variety of electrophiles usually afforded mostly

29

y-substituted

products

like

173 [ZOZ]. Li+ .++

+,

Li

OSiR3

OR

Metalation

of propargylic

banion which reacts Hydrolysis

of

& P

174

Certain

acetal

with alkylating

the resulting

as if

illustrated

z,fi-unsaturated

Phi-‘-\e

derivatives

of D-arabinose of

a car-

175 [203]. esters.

175 and D-fruciose

to cause the elimination

by the conversion

gives

it were exclusively

yields

q/-

with n-butyllithium

The process,

174 by n-butyllithium/TYEO4 agents

ketone acetals

0-isopropylidene

‘been reacted

173

172

171

170

of acetone

176 to 177, apparently

have [204]. involves

ring metalaiion.

?H

HOCH2$H-CH=CH-C(C,H9)2 OH 177 Lithiation Phinyl,

of

178 and phenylated

PhenYlsulfonyl,

derivatives

1.2-epoxyalkyllithium

rea9ents

densed with

of electrophiles-

a variety

where R is a silyl,

and cyano stereospecifically

ethoxycarbonyl,

Such reagents

179 ~205.206].

phosaffords

have been con-

178 Choice of lithium gives

of solvent diethylamide

has been found to be very important in the interaction For example, 180 epoxides [207]. with -.,,S-unsaturated

181 and 182 in ether

182

181

180 Q-Ketosulfone

and HYPA, respectively.

183 has been converted

by LDIPA, then alkylated

to its

by 1,3_dibromopropane

corresponding

[208].

diiithio

salt

Subsequent cyclizations

30

via either

C- or O-alkylation

similarly

been prepared

then condensed with cyclopentanone

acids,

Dilithio

are described.

from the corresponding

salts

sulfinyl-

to afford

-f-lactones

Other sulfur-containing

organolithitun

reagents

prepared

the parent compounds have been 186 used in the synthesis 187 used to prepare monothioglycols

[Zll],

PhS or Ph2P0 used in the synthesis

[209]_

185

184

183

Z=

184 and 185 have

and sulfonylpropionic

and acyl

of certain

by metalation

of pillarose

anion equivalent

ketones

12121.

FI &H2Li

CY ‘\

Lid A full has appeared

L-2131.

SCH., J

187 the preparation

186 paper describing

189. prepared

Species

butyllithium. was condensed useful reactions_

with a variety

by metalation

Hydroxytin taining

reagent

190 with n-

in synthetically 0

been converted with alkyl

193 [214].

of a-vinylbenzyl

189

190

by reactions

compounds to afford

the conversion

anion

Ph3P a

191 has possibly

as evidenced

of ylide

+

189

butyllithium

Li

of ylide

of electrophiles

Li

188 u&-e

188

and reactions

0 Ph3i&

of

[ZlO],

A full

alcohol

to dianion

halides

192 by n-

and carbonyl-con-

paper appeared which discussed

to a dilithio

salt

[215].

OH

H--c H

Sn(n-C4Hg)3

H

191 A variety afford

species

trophiles

i

H_ 192

of nitroalkanes like

to give

194 [216]. 195.

193

have been doubly metalated Such reagents

by n-butyllithium

were condensed

to

at carbon with elec-

31

R-CH-X02 ; 195

194

Finally,

organolithiun

reagent

196, prepared

equivalent

derivatives

number of

to give

Organolithiuns

similarly

obtained

j

:,, R

-.

aryl)

\

Li-

Compounds like

R

by t-butyllithium

[221].

202 was demonstrated

netalation

In another

of ene-sulfides

ated faster

study

versus

than the latter

predominated

290

That such reactions

to sulfur

203.

0

which contain

talation

to afford

ones [222].

Vinyl

occurred

by condensations

involvinq

ene-ethers,

both alkyl the site

a comparison

me-

regiospecificalwith electroof the rates

of

rather

than ally1

metalation

with such ene-sulfides. E

203

202

201 In contrast hydrazones like

1

RSC=CHOC2HS

RS;=CHOC2HS

RSCfi=CH0C2HS

to References 190-194. interaction of branched :1&dimethyl204 with lithium in diethylanine/benzene/HMPA affords nitriles

presumably via vinyllithium densations

(or aryl)

of vinylic

the former compounds were metal-

Li

eliminations

like were

Li -i

,R

to determine

ly alpha philes

and 2110 [220]

199

have been studied

to give

afforded

species

?!\_/4

3.’

201 (R = Ph, n-CSHl,)

groups

to yield

forma-

and ketones_

I’ ‘,

198

and alkoxy

Com-

of a large

with LDIPA at -100”

of electrophiles

with aldehydes

atom of

Thus, treatment

0

2’

197

thio

the sp2-hydrogen

carbanions.

5

I! \l/

E-

[217].

carbanion.

199 (R = C1f20CH3and CR3) [219]

and reacted

5

Li-'

of

(R and R’ = alkyl,

197 which was condensed with a variety 193 CZlR].

to a formyl

rretalation

unmasked acyl

formar;ides

of the parent

to aldehydes

XITROGE:i

Three papers described nide

by netalation

ihen oxidized

compound by LDIPA, has been alkylated pound 196 is thus synthetically E_ AT so2 C4RBO;lAXD AT

196

reagent

with a-hydrogen5 with alkyl

halides,

205 [223].

underwent in situ aldehydes.

The product

metalation

ketones.

nitriles

from such

as evidenced

and epoxides

[224].

by con-

205

204 Diazo compound 206 has been metalated 207 [225]_ tones

This lithiated

to afford

species

208 (65-8OZ)

by n-butyllithium

has been reacted

at -100”

to give

with benzaldehyde

and ke-

which has then been converted

to epoxides

and al-

dehydes _

OH

298

207

206 Theunderlinedallenic ated by n-butyllithium

hydrogen atoms in compounds 209-212 and subsequently

replaced

by alkyl

groups

H

Y qzC’C’$JHOH

have

been metaf-

[226,227].

,CH20H

‘C=C=C \

H’ =

ti

CH3 210

209

? tH3 (RO)*P-N-C;&* 211 Terminal acetylenes with n-butyllithiom ides

to afford

electrophiles lithium

214

with propargylic

to give [228].

hydrogen atoms have been dimetalated

213 which reacts Such alkylations

at the terminal

carbanion

systems have been condensed

regiospecifically are

to yield

with cuprous

to give octamethylcyclododeca-1.3.7.9-tetrayne [230],

respectively. Li

RA

*

213 Turning

stituents

[231].

by reactions

215.

Other acetylenic

chloride

[229]

and acetic

acid-D-d

RA,

‘E

’ Li compounds,

by n-butyllithium

The following

to

214 a large ascertain

order

other

carbon-

R’

RA, . Li

hal-

uith

and monodeuterioacetylene

R’

to aromatic

were metalated

with alkyl

followed

number of a ranking

215 p-substituted of

has been established:

anisoles

ortho-directing

-S02N(CH3)2.

-S02NHCH3, -CONHCH3,-CH2N(CH3)2 =- -0CH3 > -CH2CH2N(CH3)2. -NME2. -CF3. F.

sub-

33 Similar

results

The effect

were established

of TMEDAin such directed

.A regiospecific

route

o-metalating

and hydrolyzing benzamides

several

was studied.

aryl

ketones

the carbonyl

with n-butyllithium, been o-metalated

has been effected

by

group of :i,:i-dimethylbenza-

condensing

The mathod is illustrated

[232].

have also

o- and m-substituted-anisoles.

metalations

to o-substituted

reagent, = across

adding organolithium mides.

for

with various by 216,

and condensed

electrophiles,

217, and 218.

with electrophiles

Thioto afford

219 [233]. LiO

5

0

R

LiO

R :I(CH3)2

Metalation

of several

has been shown to give ganolithiun

reagent

parent methylenedioxy

220 [234].

223,

of these

lithiated

The site

with dimethylaminomethyl. of the ring

stituted

thiophenes

Z,!i-disubstituted mediates

225 [237].

metalations

of thiophenes

and carboxamides [236]_

substituted

was shown to be a Thus, 2- and 3-sub-

in the 5- and 2-positions,

systems were metalated

[235].

with electrophiles.

of the substituents

were lithiated

were condensed

Other directed

directed

Or-

exchange of the correspond-

to 222 at ambient temperature

were condensed

methoxymethyl.

position

compounds by n-butyllithium

and 222 L-2351, respectively_

from metal halogen

isonerized

species

of regiospecific

function

221 [234],

prepared

ing bromo compound at -78”. All

219

218

217

216

respectively;

only at the 3-position_

Such inter-

with electrophiles-

metalations

methoxymethylferrocene ,N-Ph Ph2P_--

224

have been effected [238],

on imides

and ferrocene

225

like

226 to give

224 to give 227 [239].

34

227

In other work dealing duced by reaction of

with metaiation

I-methyl-5-methoxyindote

tive

giving

1inked polystyrene

organolithium

has been ring

and chromium species

followed

[241].

Also.

cross-

with n-butyl f i thium-WED& [2-‘2-2541

228 has been converted

with t-butyltithium

and 1ithiation

has been found to be nonse!ec-

intermediates

t i ttiated

benzyne has been oro-

with LiTXP [240]

with n-butyllithium

three different

metafation

of aromatics,

of phenyl benzenesulfonate

to 229 (G = Si:,

by condensations

CO2Li, others)

by

with electroohiles

[245]. (Ph)Cr(C6F5G)

(Ph)Cr(C$5H)

229

228 Metalation give

231 to afford oxide, [24S].

of arylsulfonylhydrazones

vinyllithium

reagents

like

232 have been realized

aldehydes,

ketones,

230 by organolithium to be studied.

with dimethylformamide

and alkyl

X-!iHAr

R

like

231 continues hatides

[247],

[246],

)I

to give

like

233 have been treated

234, apparently

via ring-opened

Other examples are cited.

233

232

231

a-Epoxytosythydrazones phenylcopper

YE

Ri

R’ 230

carbon di-

PA

ji R>

to of

and chlorotrimethytsilane

R\;/Li

/

reagents

Condensations

234

with n-buty3lithium intermediate

235 [249].

and

Other re?+ted chemistry olefin

tosylhydrazone

of this

formation

functional [250],

methylbicyclo[4_1_l]oc afford

chemistry

the use of

this

ta-2,4-diene

diethynylcarbene

235 [252]

volving

the conversion :

for

nitrogen-containing Sy metalation.

ketones

aive

carbodiinides.

5.

LITljIUW

Lithium dichloroalkoxides

245 [260].

XD

while

to possiblv control

[25”],

239 [256]

dianion

242.

to give

Carbenoids

studr

(CH)12

hydrocarbon

R-X

242

at

170-209

nonto

O?.GR~~OLITHIiiYS

Subsequent

and the

treatment

a convenient

243 and 244 have also

Lithium dibromomethide

have also

donor and reduces

242 (X = Br) [259]

RUX’ x

and 249 [257],

have been added to ketones

241 [253]_

like

to afford

of an unusual

241

of mi-

and in a

1&C! decomposes

HALCGE!4-SUESTiTiJTED

and dibromomethide

and aldehydes

X

of

of 7,7-di-

238

species,

OTHE3

silylated

respectively_

the synthesis

bridge-bending

(X = Cl) or LDIPA (X = Br) provides like

with ketones

pyrolyses

Reagent 239 is a hydride

to alkoxides

CAP.fiEFOIDS

dihaloalkenes

[251],

237

iwo other

n-butyllithium

in the preparation

of 237 to 233 [255].

236

resulting

reaction

with the stereo-

to the regiospecificity

and to study stereoelectronic

12531 and as part of a test

been prepared

relation

fro::; *:-pinene

gration

enolizable

has been concerned

group and its

route

with to l,i-

been condensed

and vinyl

sulfides

has been employed ES part of [261]. CHO 25\::

/

C,H5D

\8rBr 243

Li

in-

36

c2*50,: SPh

/p X Cl

C2%0

A variety noids

\Li

of cyclopropanol

derivatives

Thus, treatment

[262-2641.

amides [26_3]. and 2-chloroethyl with large

[264]

numbers of alkenes

246 have been prepared

of 247 where R = alkyls

and acetylenes

to afford

246.

In the area of cyclopropyl 251 [265].

In a related

The preparation

study,

exchange [266].

Other examples of this

alcohols

addition

or diethoxymethyl,

then alkylated

of copper

249 (R = Irethyl,

via nucleophilic

Br

249 (R = vinyl

carbenoids,

to 250 by t-butyllithium,

by methyllithium cyclopropy?

248

247

R’ = H) has been converted cussed_

and

Li ROCCl2

246

to give

via carbe-

esters

with LiTMP gave 248 which were condensed-

RO u

lyzed

[262],

reagents

or hydro-

from 251 is dis-

R’ = COCH3) was converted

to the carbonyl

stereospecific

to 252

and halogen-metal

synthesis

of o-bromo-

are cited. Li

8r

R”

8r

Br

Br

LR: &y .&R &c*3 I< .R*

251

250

249

Carbenoids

containing

pared from 8,8-dibromo-

c2711. others

were thermolized

reagent

annelated

tyllithium

[272]-

[269] to six-,

OH

been pre-

or converted

Cyclization

have been realized

[267,

2nd nonenes [270].

seven-,

were condensed

and gemi-

and eight-membered

with

electrophiles

rings

while

to allenes.

253 has been generated

and a dichlorodisilane

cyclizations

have similarly

and 8,8-dichloro-3.5-dioxabicyclo[5_l_O]octane

Some of the above species

Organolithium

252

endo-lithium-exo-halogen

266].9.9-dibromo-cis-bicyclo[6_l_O]nonanes nal dibromocyclopropanes

\

followed

from the corresponding

by metal-halogen

of 253 led to 1.2-disilacyclopropane on bis(sily1)

bromolithium

exchange with n-bu254,

Other

system 255 with dimethyldihalo

derivatives of silicon, germanium, and tin to afford 256 [273].

3i

si\SiLC’ \

‘Li

254

253

257

256

258

(M = Si.Ge.Sn) Finally, to give verted

lithium

dichloromethanebot-onic to 258 by mercuric

to be useful

acid

has been condensed [274],

and vinyl

bromide [275]_

in transferi-ing

with trimethylborate

system 257 has been con-

Mercury reagent

isopropylidene

carbene

253 has been shown

to olefins.

ADDITIO:: AND SUBSTITUTIONREACTIONS

6.

A simpler dardization

method :han double

of alkyllithium

through a syringe acetic is

dichloromethide

acid

solutions

of butyl-

in THF until

titration

has been suggested

[276]_

tire yellow

procedure

ihe

or methyllithium

for

the stan-

involves

addition

to a weighed amount of diphenyl-

end point

due to dili+hiodiphenylacetate

reached. In the area of aliphatic

lithium

initiator

two equivalents

soluble

and aromatic

of n-butyllithium

The initiator

organolithiums,

to one equivalent

alcohols

alcohols

to give

allenic

lithium

to 261 and subsequent

of styrene

259 have been found to react

269 [27G].

Similar

hydrolyses

additions

to ally1

di-

by adding

of m-divinylbenzene

has been employed in the polymerization

Alkoxypropargylic

an efficient

in benzene or heptane has been achieved

with n-butyllithium

of butyl-

alcohols

[277].

and isoprene. and benzyl-

are discussed.

CH30 R+

=

R’

OH 261

260

259

Both ciscloalkenones

Fh----

TOH

and trans-lithiocyclopropanes

262

such as 263 to give vinylcyclopropanes

Functional ized

cycloheptanes

are thenobtained

have been added to alkoxycvsuch as 264 L279]-

by heating

264.

3s

OR

Tandem phenylation further

investigated

ketones trated

264

263

262

by phenyllithium-reduction

as a method of converting

to S,v-unsaturated by the sequence

aromatic

by lithium/amnonia %,2-unsaturated

hydrocarbons

has been

aldehydes

The process

[ZSO].

and

is illus-

265 - 266 - 267.

266 Phenyllithium to afford

and related

ketones

like

reagents

268 and esters

ed to z,.,“-butenolides

to give allylic

tain

at sulfur

sulfonate

boxylic

acids

esters to afford

sulfones

and carbinois

the nitrile

triple

via the intermediacy

[283],

[284],

Ar

/i

Ar’

and added to an aminoketone [285]_

by addition

In contrast

and methyllithium

Such reactions

In a different paper, ketones and non-enolizable nitriles [287].

R-k-

R-LNLi h

N\

lb- /

r

N‘Li

to earlier tetraene

results,

condensation

and diazomethane 275 [288].

proceed were syn-

&-’

273

272

_

with carbon dioxide

274 and non-cyclic

of butyl-

[286].

NH 271

with cer-

combined with car-

of 272 and 273.

NH

been add-

reacted

270

bond of arylnitriles

from pyridyllithiums

R-\t lithium

They have also 270 [282],

269

Enamidines 271 have been obtained

thesized

like

ofdibenz[b.f,l]azapentalenes

268

across

269 [281].

alcohols

to yield

ketones

as part of the synthesis

have been added to perfluoroanhydrides like

of cyclooctatetraenedi-

has been shown to give

tricyclic

39

275

274 Interaction been reported [289]_

of pyridine to qive

In contrast,

pyridine

reaction

gave mostly

:*ith those

obtained

278.

with metal-free

P-n-butylpyridine

n-butyllithiun

(276)

between n-butyl

277 and less

chloride

than 1% of 276.

and lithium

The results

Derivative

with magnesium species. l.fi-

in pentane has

but no 4-n-butylpyridine

metal in

are compared

277 might arise

from

. -.

_ ‘,

A

$+..A,

,i

W

Q

V

(277)

t ‘I

Li

276 Cyclic thioethers attack [290].

at sulfur

like

by t-butyllithium

The driving

force

for

to afford

such reactions Attack

benzhydr:;l ic carbanions

1i ke 281_

been realized

282 and its

dioxide

on thiete

derivative,

phinodithioate

esters

respectively like

278 ones have been found to undergo

277 279 and related

is ascribed

at sulfur

l,l-dioxide

[291],

ring opened products

by organolithiums

tc give

283 and its

and at the alkylthio

284 to yield

phosphine

sulfides

sulfur [292].

fi

,

..

\

I Ph279

Ph 280

281

Ph2P-S-R 5 282

like

280

to the stability

284

of

has also related of phos-

40 Epoiyethylsilanes tetraphenylsilane was determined

like

diisobutylaluminum

g-alkoxysilane acid

and anti-elimination

_.

J\

288 and 289,

respectively

12943.

arose

(RI” Li)

in THF or ether while

respectively_

is a function

of solvent

289 and ketals

[2g5]_

Thus, 291 OSiI

0

RARm*

R”

R’ ”

290

A variety

hemithioacetals

292 is formed in HMPAor TMEDA.

OSiz

SR

acetic

from syn-

L

288 of 0-trimethylsilyl

of reaction

(290) with organolithiums is obtained

jugated

or glacial

The olefins

R

287 The course

R+

an intermediate

t-butoxide

R)& Si;

using

:Ph

286 287 afforded

to 9-ketosilane

of hydroxy and trimethylsilyl,

+

and trans-286

0

which upon treatmen t with potassium

gave olefins

it

alpha to silicon

on both cis-

amines.

\

285 of methyllithium

Addition

to give

of 285,

are compared with those obtained Ph3Si

?

analogues

the carbon

chemistry

The results

and various

Ph3Si J

attacked

Similar

manner.

trans.-stilbene.

with phenyllithium

Using deuterated

[293].

that the phenyllithium

in a npn-stereospecific gave mostly

285 have been treated

and styrene

of allyl-

and saturated

291 lithium

292

reagents

have been added to con-

enynes 293 where R’ = alkyl [296] and amino or hydroxyl groups [297]. products obtained such as 294 are in contrast to 3.4- and mix-

The 1,2-addition tures

of 1,2-

and 1,4-addition

and magnesfum reagents,

products

realized

with corresponding

respectively_ R

organozinc

R

R”

_--

*i*

Condensation a+-dihaloalkanes

293

of dilithiobutadiene

and other

have been found to give

cyclic

di-

294

and triene

products

tion

at the most negatively

charged carbon atom followed

tion

to afford

ring

the smallest

possible

[2g8].

from 296 and 1,3-dibromopropane.

In other

been employed in the synthesis

of monoterpenes

ium has been added to benzyne addition products [300].

by secondary

For example,

papers,

dianions

from initial

alkyla-

295 is obtained

pentadienyllithium

12991,

with alkyla-

297 has

and cyclopentadienyllith-

to give phenylcyclopentadiene

rather

than cyclo-

=

0

__ - -. -._ 2LiC (4

295

A variety Among those

of annulenes

continue

to be synthesized

formed were 1,8-bisdehydro[14]annolenes [302-3051,

addition

with lithium

298 [308].

In contrast,

specific;

for example,

erythro

ratio

_-

giving

similar

a lrl

additions

the latter

reagent

have also

afforded

with a threo-

pyrimidine

derivatives

like

of certain

enolates

vinylogous

derived

the conversion

300 with chlorobenzamides

302 [309],

prostaglandins

in HMPA/benzene/ether [314].

like

trihalides

have also

been

[311,312].

303 by carbonyts

and other

electron

304 have been synthesized Such reactions

[313].

Methyl ethyl kinetic

like

and with Group ‘J

Such organolithiums

from 305 and ketones to their

) 32

ii

stabilized aldols

of 306 to 304.

been converted

6-hydroxyketones

y’jN(Cii

302

Turning to organolithiums groups,

0

been condensed

301

have also

alcohols

the cis-alcohol

Li

303 (M = P, As, and Sb) [310].

employed in the synthesis

tute

of the cis-trans

299

Lithium acetylides

kinetic

and

of 299 and 300 were more stereo-

ijOLi

-Y

298

withdrawing

[306],

of Sri_

Ph

to yield

acetylides.

was found to be non-stereospe-

mixture

0

301 to give

lithium

6,8,15,17-tetrakis-

[307].

to 2-phenylcyclohexanone

acetylide

using

[307],

a 6,17,23-trisdehydro[ZZ]biannulene

a 2.4.13.15-tetrakisdehydro[ZZ]annulene Carbonyl

Lif

207

295

dehydro[18]annulenes

cific

(&AJ-

enotates

and methyl propyl by lithium

and then condensed with aldehydes

using constiketones

diethylamide

and ketones

to give

0 i’

OH R6

A/+‘.

CH3- =

R”

R

The enolates annelating enolate

of several

reagent

to yield

310 via C-alkylation gave only 0-acyl

Sulfonium ylides butyllithium variety acids

been

[320],

The chemistry

of aldehydes. by certain

have also [319],

halides

of 309 with acyl

to yield

ketones,

esters,

to 312 by

313 [317].

nA

and carboxylic chlorides

and sulfenyl

sulfur,

disulfides,

313

and used in the total of dilithio

than y-products

( 2 fb - \..

and angelic

= 2Li+

0

1

illustrated In contrast,

acid acids

[322].

halides

anhydride

catalyzed

to give

of sativenediols

of a.&unsaturated

317.

314

by nethylene

synthesis

only y-products

and 3-methylcrotonic

c/”

salts of salts

317 [322,323].

gives

tiglic,

been alkylated

condensed with citraconic

Thus, alkylation

in such reactions

_&

and acylated

312

be studied.

R

with alkyl

reaction

314 [318].

butenolides

c-

has been treated

In contrast,

[316].

enolates

Ketone enolates

butynoic

(309)

with bi-

The lithium

311 (R = CH3. OC2D5) have been converted

thiolated

by cuprous chloride

senecioic,

have been condensed

compounds 308 [315].

derivatives0

311

H

tricycle

or LDIPA. then alkylated

of lithium have

to afford

(316)

cyclohex-2-enones

307 to afford

of cycloocta-2,4,6-trienone

chlorides

306

305

304

acids

continues

by 315 afford

studied

and 3-methyl-2-hexenoic,

[323]. R

k R’7 316

cuprates were 2-

crotonic.

R R>,/.

C02CH3

C02CH3

315

to

more cr-

the use of lithium

Among the acids

two

[321].

317

43

Trilithioitaconic

acid

to afford

u-nethylenelactones

similarly

been reacted

6-n-hexadecalactone

(318)

has been condensed with aldehydes

like

319 [324].

with certain

chiral

Dilithiopropiolic

epoxides

to give

and ketones

acid optically

(320)

has

active

[3X].

Li C02Li

Li02C

Li

ADLi

-EE

D. 318 Related 3273,

319

salts

coupled

of acids

have been oxygenated

with formaldehyde

Monoalkali

[329]. esters

320

carboxylate

[3X3].

with molecular

and condensed

anions

oxygen [326,

with carbon disulfide

have been directly

alkylated

A full of esters

paper appeared describing and ketones

cycloheptancne

(321)

[331].

sulfenylations

The process

and dehydrosulfenylations

is illustrated

by the conversion 0

SPh sodium meta-

LDIPA PhSSQh

periodat?

)

322

321 Lithium enolates bromomalonate

esters

by displacement

bine by conjugate

323 Benzylidene yield

of

to enone 322. 0

occur

to yield

[330].

of alkylidene like

succinates

324 to give

products

(323) like

of 323 on bromine to afford

have been condensed with 325 [332].

malonate

The reactions

anions which recom-

addition-elimination.

325

324 derivatives

of glycine

326 which can be alkylated

to give

esters

327 [333].

to 328 thus finishes

the overall

Potassium

may be employed instead

t-butoxide

have been lithiated

conversion

by LDIPA to

Simple hydrolysis

of “glycine” of LDIPA.

ph_--.z

Qfy-F.=

R 326

327

of 327

to higher a-amino acids.

328

f-l

Several cinimides

a-ltthioesters

like

and nitriles

329 to yield

papers, ethyl lithiofarnesoate oxygen and a-thiomethylation lithiodiazoacetate

products

0

C02CH3 I

o-~~ 1 ‘I’”

330 [334].

has been found to undergo a-hydroxy?ation

CH2G 0

[335],

with

and ethyl

332 [336].

c& d BF4-

N2CC02C2H5

330

331

332

derived

from phosphorus

esters

and amides have been employed

Reagent 333 has been condensed with 310 (R = H) as part of the syn-

as follows.

of a 1,5-methano[lO]annulene

system [33?]

and reagent

334 has been added

to ketones taining

suc-

In other

C0*CH3 329 Organolithiums

like

with methyl methanethiosulfonate

has been added to 331 to afford

&zA

thesis

have been added to N-protected

polyfunctional

as -part of a new spiroannelation leading to quaternary Oiethyl-l-‘alkyl-2-oxoalkanephosphonates cyclohexanones [338]_

prepared

by alkylation

a-copper

reagent

of 335 followed Finally,

[339].

been found to be stereoselective depending

upon the solvent

by acylation

condensations and give

of a subsequently

prepared

of 336 with acetophenone

different

and the presence

carbon-conhave been

diastereoisomers

or absence

of

lithium

of

have 337

bromide [340]_

0

334

333

;

335

Li

(CH3)2N’pl+ph cH3 337

336 N,N-Disubstituted by lithium

amides and N-substituted

dialkylamides

in HMPA, then alkylated

and 339, respectively

[341]_

selenenylated

products

to give

Lithiolactams like

lactams

have also

340 [342].

have been a-lithiated

to afford

species

like

been sulfenylated

338 and

Reaction

of

posed to yield

340

339

338 lithioacetonitrite

intermediate

and retated

compounds with 341 has been pro-

Some chemistry

342 [343j.

of 342 is discussed.

Li+ -tr(C0)3 342 Other tithionitriles sitytated

[348].

have been hydroxylated

and employed in the synthesis

%-Metatated

isocyanides

hydes and ketones

to give

to 345, methanotysis

like

R = hydrogen, like

of which yields

‘and R’ =

343 have also

343 (M = Li,K)

intermediates

pyridyl

,

been condensed

and with carbon disutfide

to give

affording

347 which,

to 346 when M = K,

formamides

to yield

[351]. affords

.

343

344

345

346

347

348

Under the topic like

[352]

348 [353].

M

=c

of miscellaneous

of nitro

lithio-2-nitropropane

nitrosopyrrolidine

Species

3-amino alcohols

upon methytation,

M

the displacement

with alde-

compounds cyctize

Both 344 and 345 have been

345 is converted

with epoxides

[346,347].

[349].

The latter

P-oxazolines.

ultimately

atkytated

have been condensed

344 [350].

In contrast,

trapped with electrophites.

[344,345].

of S-cuparenone

(349)

nitrogen

groups of p-substituted

compounds,

synthetic

nitrobenzenes

in tMPA have been published and 2.5-dialkyl-N-nitrosopyrrolidines

[354].

details

of

by reagents a-Thioethyl-Nhave been syn-

-16 thesized fide

from the lithio-N-nitroso

[355]

and alkyl

of products

arising

halides

compound and ethyl

[356],

respectively.

methoxycarbonyl

Finally,

dtsul-

the wide variety

from dilithio salt 350 and certain acid chlorides, chloro-

acid chlorides, and chloroesters has

been described

[357]. ki

Ph2C-NPh Li

Turning to sulfur-stabilized been conveniently-metalated condense w=ith aldehydes are useful describes

organolithiums.

by LOIPA in THF-HMPAto give and ketones

to afford

in the synthesis

of 1;4-diketones

the use of 353 for

cyclopentanone

of an earlier

method such as low yields

lithium

[360],

(354)

351

of vernolepin

fonates

of primary alcohols

reagent

[363].

Phenylthiomethylhave been used

to afford

of fraudulent

branched-chain

sugars

respectively.

355

354 alkylated

added to 356 to give

fluoroborate

351 which compounds

in which the limitations

355 [361,362]

353

358 [365],

have

Another paper

and cyclcpentenones. formation

have been conveniently

with-tropylium

like

The latter

and n^-phenylthioketones,

352

P-Lithio-1.3-dithianes

sulfides

species

352 [358].

are overcome [359].

and bis(phenylthio)

to prepare a precursor

phenyl vinyl

with arenesul-

357 [364],

condensed

and employed in the synthesis

from certain

ribofuranosides

[366].

OR’

0 356 Monolithiated

s-trithiane.

357 tetrathiocane,

358 and pentathiecane

2, atid 3) have been condensed with carbon dioxide, disulfide

to give

sulfur

‘CH-5/ 2

(n = 1,2,3)

n = 1,

and carbon

360 [367]_

s/(CHrS)o\CHLi 359

(359,

dioxide,

360 (I-I = 1,2,3)

(S02Li,

CS2Li)

Lithiodithiane

361 adds

in a l&fashion

362, a compound

which

subsequently

alder

[368].

Dithiane

reactions

ketones

to give

conveniently

enters

361 also

ketene thioacetals

converted

ii

into

like

CH3

to afford

condensations

The latter

and Diels-

aldehydes

and

compounds are

with NCS or iiBS.

CA

361 Interaction

into Michael

has been added to other

363 [369].

n-haloesters

Si:

to Z-nethoxyacrolein

363

362

of 364 and 365 has been shown to afford (RI- and (S)-4-hydroxyFinally, tris(methylthio}methyllithium (366) has been [370].

2-cyclopentenones

employed in the synthesis

of dl-protolichesterinic

acid

[371].

CH3S

Li CH3SO/

Lithiation

of epoxysulfones

368 [372.373]. stead

Interestingly.

of n-butyllithium

Epoxynitriles

like

367 leads

metalation

to cyclopropyl

cyclobutyl

products

of l,l-dilithio

ii

[379]

have been alkylated

and with epoxides

PhS02XPh

Li2CHSON(CH3)2

like

372 have been converted

371 to a-selenoaldehydes

373 (G = R) by acid chlorides, 373 (G = 0CH3) by methyl chloroformate , and to a-selenoacids

OH) by carbon dioxide ketones

ultimately

and con-

[380].

373 (G = H) by OMF, a-selenoketones esters

[375-3781

Li

370 a-Selenoalkyllithiums

[381].

affords

in-

369 [373].

systems 370 and 371 has been reported

of monolithiosulfones

densed with carbon disulfide

like

369

368

A variety

like

[373].

367 chemistry

derivatives

of 367 with methylmagnesium iodide

or LDIPA affords

behave similarly

Additional [374].

366

365

364

Similar

treatment

a,B-unsaturated

a-seleno373 (G =

of 372 with a,?-unsaturated

epoxides

[382].

4s

I

R” Li

G

RSe%

0 373

372

Methoxyvinyllithium denced by its

reaction

(374)

and 3-hydroxy-2.4-pentanediones lithium

(375)

the first

has

been

A / esters

with

like

halosilsnes

C- or S-alkylated

products

afford

381 is described-

[388]. to yield

Lithium reagents

is observed

to give

to nive

employed [387].

380 with several

epoxides

to

The related

trimethylsilyllithiun

381 [389].

Subsequent chemistry

382 (M = Si.Ge.Sn.

of

and Pb) have been cou-

383 in which retention

of the double

bond

[390]. R3MLi

:M

OLi

n.-.-

HETEROCYCLES Several

large

Lithiosilyl-

have been alkylated

upon the electrophile

has been condensed

olefins

chlorides

alcohols

to the corresponding

379

has been added to cyclohexenones

7.

hydrolysis,

376 to sive

was studied.

by metalation,

depending

Dimethylphenylsilyllithium stereospecifically

/

after

with aldehydes

of the reaction

378

377

Zji n.

[333]

ethoxyvinyl-

0

compounds were converted

and the stereochemistry

configuration

afford,

376 [385]. Li

379 and amides 380, prepared

pled with crotyl

to

as evi-

dihydroxyacetones The related

respectively-

375 377 has been condensed

The latter

378 [386].

chlorides

condensed

to give

OCH3

374 Lithiovinylsilane like

and esters

[384],

stable acylsilanes Li

to b e employed in synthesis

continues

with ketones

papers discussed

number of N-substituted

nicotinic

acid

to determine

derivatives

the extent

certain 1,2-,

aspects

have been treated and position

of dihydropyridines.

1,4- , and 1,6-dihydropyridine

Thus, a and dihydro-

with LDIPA and potassium

of metalation

[391].

Although

t-butoxide

the pyridine

49

derivatives afforded

gave little vinyl

or no metalation,

organolithiums

denced by deuteration Li

like

@yR

p-

c kH3-‘Li 385 1.2-dihydropyridines

384 In contrast, V-unsubstituted and the anbident

pyridines

organometallics

like

alkyl-1.2-dihydropyridines

388 [392]_

involves

with

Incidentally.

the conversion

sized

by alkylation

reduction

The direction

is discussed.

and aryllCthium

of base-cataly

In another

to.afford

and temperature

54ithiouracil

either

derivative process

394 34ethylquinoline THF-HMPAto afford

FM-

p

78

-T \

Li

390 xhich. have been synthe(391)

zed aldol

2,2-bipyridyl

followed

cyclization was treated

392 OF 393 as a function

by Birch of such di-

viith alkyl-

of the stoichiometry

- 393

394 has been found to rearrange

to 395 [396].

rearrangement,

cause of the high electron OSiz

to give

[393].

392

an intramolecular

halides

paper,

to give

of :I-

i395] _

391

went a similar

389 o f 1,5-diketones

of 2-lithiomethyl-Gnethylpyridine

[394].

ketones

electrophiles

a new synthesis

i0p3

388 a series

387 paper described

CH3 386 387 have been I:-

of 389 to 330 by methyllith-

the corresponding ii-alkyl derivatives /- *‘.<, E/' fl ‘I ,-= C .. :;,.A; ci, '\,& :;., ,.' A

. ._st...‘.x Li

like

condensed

ium and heaxing

ii

1

H !

it

i

CH3

A full

compounds

and CR) as evi-

H

-. Y’--‘.H

s-substituted

acid

(R = carboxamides

experiments.

i,H

lithiated

the dihydronicotinic

384-386

Although

dilithiocytosine

density OSiz

397 was stable

for

396 the first

OSiz

397 time using LDIPA in

398 which was condensed with aldehydes. Similar

treatment

via

396 under-

presumably be-

on nitrogen. LiNSiz

395 has been metalated

399 [397].

apparently

dilithioisocytosine

ketones,

and alkyl

of cycloalkenoisoquinolines

400

50 yielded

mostly metalation

when n = 5,6 [398]_

products

In contrast,

401 and little large

or no addition

products

amounts of 402 were realized

402

when n =

398

&-Jy

@qy -4

>i

Li 403 has been metalated

to give 404 [3g9]_

followed

by condensation

Ph

402

401 Tetrahydroisoquinoline kylated

;“’

Metalation

of either

with aldehydes

by n-butyllithiun,

then al-

403 or 404 by sodium hydride

and ketones

afforded

405.

::J-6Jq* ::Jx---qj RA

‘P(OC2H612 // 0

monolithio

(406)

or dilithio

by treatment

two equivalents

of LOIPA in THF/HMPA[400].

afford

a variety

aY 0

Perimidines mostly [401]_

products

405

(407)

may be prepared trophiles

P(OC2H6)2

404

403 Either

// 0

0

like

of 2,3-dinethylquinoxaline

of the parent dimethylated

heterocycle

Subsequent condensations quinoxalines-

of 2,3-substituted CH2Li

o

LCH

with one or with elec-

! ;ycH2Li

T‘f \wlCH2Li

3

406 like 408 react

In one case,

salts

with alkyl

407 and aryllithium

409 which arise

by addition

ring

occurred

lithiation

reagents

of RLi across

to afford

to give

the C=K linkage

410 in low yield.

51

408

409

An unsuccessful bases

like

desired

attempt

phenyllithium

412, mostly

410

411 to 412 via 413 by means of strong

to convert

has been reported

411 was recovered

despite

ArChzlJ

ArC”=llufl 0

by metalation,

cyclized I

is higher

‘C02R

cyclizes in their

by copper(I1)

413 to 415 with or without

presence.

The related

hydrolysis

copper(I1)

non-benzo

sys-

415 acid

but not LDIPA, to give electrophiles

Lithiated

‘C02R

’

fluoride.

4,5-Dihydro-1.3-thiazoli-4-carboxylic

Thus, a full

zn

have been described [403].

414

with various

the

by D20-CD3C02D.

412

prepared

n-butyllithium,

of obtaining

ArCn=f

examples of heterocyclotetraaromatics

salts though the yield tern was also

quenching

rfi

411 Thus, 414,

Instead

0

‘C02R

Additional

[402].

416 oxatolines

to give a-substituted

has been dimetalated

by

Subsequent condensations products

are described.

417 continued

paper described of which affords

(416)

417 [404].

to be extensively

the alkylation

oi chiral

S-o-alkylalkanoic

acids

investigated

in 1976.

system 418 to give 419. 420 in enantiomeric

purity

52 of

45-85% [405].

alkylation

of 418 (R = H) gives

order of introduction yields

sequential

Interestingly,

(S)-(t)-420

of alkyl while

stereoselectivity

(R)-

halide-lithium

cation

entry

dependinq

upon the

nethylation-butylation

affords

to an underside

and two-fold

metalation

acids

For example,

groups.

butylation-methylation

is ascribed

to 418 via initial

either

two-fold

or (S)-

(R)-(-)-420.

Such

of the alkylating

agent

complexation-

Ph

=Q/

RCE

0.. 1 Lie&H3 418

419

Lithiooxazoline nition

418 (R = H) has been found to be capable

towards racemic

mides and iodides

halides

kinetically

in the R enantiomer

enriched

3-alkylalkanoic allows

are

alkyl

acids

(420)

the establishment

Thus, racemic

[406].

resolved

by 418 to give 419 which,

and oxazolines

likewise

enriched

of absolute

of chiral

secondary unreacted

alkyl

upon hydrolysis,

in the R enantiomer.

configurations

of secondary

recog-

al kyl brohalides

afford

The procedure alkyl

halides

and 420 using only 418. Chiral mine if

oxazolines

they might also

[407,408]_ anoic

Butylation

acid

(420)

[407].

of nihutyllithium

technique

of conjugate

containing E4°g]-

serve as suitable of 421 followed

though the authors

the R configuration dition

421 and 422 have been derived

systems

precursors

by hydrolysis

predicted

Conversion and hydrolysis

425 to yield

A,

to optically

the acid

should

gave (S)-f+)-424 has also

methoxyacids

to deteracid

acids

gave (S)-(+)-2-methylhexhave possessed

of 422 to 423 followed

addition-hydrolysis

like

front L-serine

by conjugate

(4081.

ad-

The iatter

been employed on methoxylike

426 and their

q

lactones

‘“=$--9+

CiCH3 421

i)CH3

422

423

Ph

424 Related 428 via

426 oxazoline

429 [410]

responding

2-brnzoyl

by LDIPA to afford oximes [412].

chemistry

included

and the autoxidation derivative

431 and 432;

[411]_

the conversion

of

of

430 by molecular

P-Isoxazolines

427 to thiiranes oxygen to the cor-

have also

the former compounds fragment

been metalated

to a,$unsaturated

R \ \ .. N-

R@-I

427

430

Metalation (436)

isoxazoles

of

and methyl group

on these

(435)

423

429

431

432

433 and 434 by n-butyllithium lithiation

f413].

yielded

In contrast,

Li

both ring-

the use of LDiPA

systems gave only 435.

o-at3

/

433

434

Oxazine deriva:ives

437 and 438 have been found to react

ketones

and aldehydes,

to afford

respectively,

Thus. 437 gave 439 while

437

434

438 afforded

with aldehydes

stereospecifically

to give

[414].

440

439

441 has been lithiated,

and ketones

olefins

440.

438

Thiomethyldithiane

436 with unsymmetrical

esters

then alkylated

or a-hydroxyesters,

or condensed resoectively

[415-J.

1,3-Dithiane-l-oxides have also been metalated and condensed with elecThus, 442 with LDTPAafforded a Z-lithio derivative arisin9 trophiles [416]. from preferential Tithio

salt

by a factor densations

abstraction

with certain of 3-4:l.

of the C-2 equitorial

electrophiles

occurred

Other stereochemical

cis

results

of 443 (R.= CH3 and Ph) with electrophiles_

proton.

Reaction

to the sulfoxide are discussed

for

of this oxygen the con-

6-l

Q

c-Jo

R

H

CH3S

A large of

l urophenes

number of papers appeared lithium

derivatives

of

to allenes

certain

2,5-dialkyl-3-lithio-thiophenes

stituted

thiophenes,

like

containing

additional

selenophenes.

446 [417].

occurs

447 (M = 5 and Se) [418-421]_

ble and do not open [420,421].

chemistry

Similar

andselenophenes

2-chloro

Such ring openings

have been employed in the

446

445

=\_

i

3-halo

compounds have also

of strong three

bases in polar

position

on the sulfur discussed. ford

been described. gives

of the heterocycle

[423].

of the side-chain

dilithiobutadiene

[424].

Condensed

to give

products

without

Thus, treatment

of

of 450 by a variety at the

Products arising from substitution and abstraction of a thiomethyl proton are

452 as evidenced 453,

454.

in which the selenium-

SCH3 450

-\,

the intervention

by condensation and 455 also

has been found to afwith electrophiles open with methyllithium

but not the sulfur-

containing

[4251_

CR3

__-

--KH24,-’

447 (R = SCH3) via metalation

of 451 by n-butyllithium/TMEDA

selenophenes

-=

449

such ring-openings

solvents

Metalation

are cleaved

.-

448

447 of

3-

groups are sta-

&Z-A, Ar

444

examples

sub-

In contrast,

Ar*Ar

other

of

to afford

and 2-dimethylaminomethyl

of 448 to 449 [422]. Li

Several

ringand tel-

444 have been found to open even

445 and ketoacetylenes

vinylacetylenes

lithiothiophenes conversion

in 1976 describing

furans.

_ Thus, 2,5-diaryl-3-lithiofurans

at -65”

%i 443

442

441 openings

Q.

Ph 451

452

rings

55

m

w Other papers

concerned

the rearrangement

gen-metal

with organolithiums of tricyclic

exchange reactions

paration

455

454

453

scribed

y-J---J

of Z-chloro-

and the preparation

and heterocycles

systems

of a variety

like

of dihalothiophenes

and 2-bromotellurophenes and subsequent

have de-

456 to 457 [426],

the halo-

[427],

the pre-

from 2-lithiotellurophene

silylation

of 458 and related

[428],

compounds

CS29] -

R’

R'

ii

457

455

1 . 456

a.

COPPER-LITHIUM Propargylic

461 merely Similar

reactions

than water.

AND 0THER"ATE"

CMPLEXES

459 have been converted

acetates

by running

Intermediate

REAGENTS

the reactions

on propargylic

ate complexes 0

acetals

462 gave ally1

like 464 have been trapped

-

like

463 [431].

by electrophiles

other

-.-R

>

I

R

111

460

459

H-

acetals

460 or

[430].

I‘

R'

R-=

by R2CuLi to either

at -loo and -SO", respectively

= \

oC2H5

462

Methyl propiolate 465 to afford

466 [432],

[433].

Similar

tylenic

ketone [433].

self followed iodides

[434],

have also been

464

463

products

has served

were obtained Related

by condensation and on allenic reported.

as a co-reagent

and to cyclopropyl

of other

electrophiles

ketones

Similar

like

using the latter

additions with

to allenic

cuprates

cuprates

cuprates

468 it-

to give vinyl

mostly

to an allenic

like

and an ace-

on acetylene

like iodine

like 469 to afford

1.2-additions

cuprates

467 to yield

470 [435]

phosphine

56

oxide

have been described

[436].

( *.+C”Li

>=.-\

2

‘P+

2

CuLi

--J

02CH3 467

466

465

=.A*-

cuprates

have also

1437-4391

and with ally1

lustrated

by the conversion

475_

halides

the interaction

Thus, 475 was realized

are il-

472 (R2CuLi) with Z-halo-

474 and addition

[444],

products

G = COR, and !? = methyl [441],

G = COR, and R = cyclopropyl

[442].

but

Similarly,

[443],

X = I, G =

and X = Br, G = C02H or C02CH3. R = methyl

[445].

ALG

A-

have also

476 to olefins

\ 0

0PO(OPh)2 i

476

475

been used to convert

like

477 C4463,

R

I

477

/”

RI

474

473 Dialkylcuprates

J

--Y/G

R

X

479 [447]_

of cuprates

when X = Br, G = COP., R = cyclopropyl

COR. 9 = 2-vinylcyci;propyl

like

acetates

The reactions

olefins.

substitution

when X = Cl,

when X = Cl,

only 474 was realized

esters

to 9ive

compounds 473 to afford

474 was obtained

and n-butyl

[440]

ally1

of 471 to 472 [437].

471 papers discussed

-x,t-unsaturated

been condensed with certain

R

0

Several

470

469

468 Various

enol diphenylphosphate

and ketones

like

478 to ones like

d’ d 478

479

Additional

examples of the condensation

with cyclohexanones alkyllithiums lithium

further

[448].

demonstrate

For example,

di?ithium

add to t-butylcyclohexanone

Reagents

480 also

tion of lithium

to increase

to afford

papers dealing

diphenylcuprate

in the presence

over

and n-butyl-

to -.,S-unsaturated

has been found

1-lrisityl-3-methyl-2-butenone

[449].

carbonyl

the rate of reac-

additions,

of triphenylphosphine;

composed by added ietracyanoethylene

480

reagents

481 in 97% and 86%, respectively_

with conjugate

with

trialkylcuprates of these

tri-n-butylcuprate

have been added in a 1,4-fashion

In other

compounds.

of dilithium

the superiority

the cupraie

is,

however,

Lithium dinethylcuprate

de-

has heen

condensed with pyranosides like 482 to a fford 453 [450], and with oxo-enones like 484 to give 485 via regiospecific intramolecular aldol condensations [451]. OH

R”@ro _

&R

”

H

480

481

482

484

485

CH3 483 Lithium cuprates furan to alcohols to sulfoxides

[453]_

regioselectively

have been found to cleave

486 {P,’ = H or CH3) [452], Lithium dimethylcuprate

added to iron

salts

THF and 2_methylte:rahydro-

and to convert

sulfinate

esters

has been stereospecifically

487 to yield

and

488 14541.

cH3

Lithium cuprates natural

products

spirovetivanes lide

were employed as part of the synthesis

in 1976 including [456],

14611.

dl-sesquicarene [463],

alkylated

recifei

side

organoborates,

on the B-carbon

[457-4591,

[460],

and dl-sirenin

and the acyclic

Turning to lithium

methyl jasmonate

prostaglandins

from Cephalosporium

cockroach

488

487

486

certain [462],

of a variety

and related

a naturally

of

compounds [455],

occurring

macro-

a-methylene-y-butyrolactones

a sex pheromone of the German

chain of several natural products [464]. a 1kynyl trial kyl borates 489 have been

by methyl sulfate,

triethyloxonium

fluoroborate,

and

58

other

active

alkyl

like 49? [455].

halides

and nitriles,

ters, tones,

y-ketonitriles,

y-ketoesters, acid

idation

Details

[467].

instead

upon hydrolysis l_i+

R3B-C-CR’

c=c

/

489

tylenes.

Similar

ployed

to synthesize

been studied prostaglandins

0

[466].

412 after

,YL I!

491

rearrangements

carbon

conjugated _

have been em-

borate

for

494 and with the

reagents

has

the synthesis

(Sia)

of

2_
c:ck*

C-CR’

494

Reagent 489 has been condensed (R” = Sn(n-C41fg)3)which, The use of other chloride

electrophiles apparently

495

with tri-n-butyltin

upon treatment

with formic like

yielded

chloride acid,

to give

affords

trimethylaluminum

491)

Z-olefins

chloride

490 and an isomer since

and

hydrolysis

of Z- and E-olefins.

Z-Brono-6-lithiopyridine afford

ace-

E471.4721.

493

gave mixtures

493 whic$ allyls,

acetylides

( G+
[473].

salts

unsymmetrical

of other

of such reactions

R3B-CX-Li

phenylsulfenyl

492

Intermediates

lithium

Iodination

suitability

R’

= alkyls.

and of 495 [470] diynes.

of appropriate

alkynyldialkylboranes

489 (R’

then affords

of 494 [469]

by condensation

to determine

to give

iodination

unsymmetrical

ox-

of 490 to 2 or E-

R”

Subsequent

es-

1,4-dike-

The use of

to ketones

R’

it

at the acetylenic [468]_

ketones

acids.

490

undergo alkylation

495 were prepared

leads

yield

489 (R’ = H) have been converted to dilithio

Boron reagents trimethylsilyl)

gives

by =-haloketones,

about the conversion

/R’ \

oxidation,

bromide to ultimately halides

by carboxylic R,

after

been alkylated

and y-ketoalkynes

of alkyl

are provided

R2B

corresponding

490 which,

and by a propargylic

methanesulfonic olefins

to afford

Reagents 489 have also

intermediates

tic

acid

treatment

for

the preparation

like

has been added to trialkylboranes 496 which decompose to vinylboranes

of 497 to give

498 illustrates

the utility

to presumably 497 [474].

Ace-

of the method

of pentadienenitriles. N

R2+ s+L CN

BR2

496

h

497

H

H

498

H

59

Trialkylboranes

have also

afford

499 which,

upon treatment

been condensed

idstion

of 500 then yields Li+ :!

with a-methoxyvinyllithium

with hydrochloric

acid,

dialkylmethylmethanols FI

gives

501.

Y

R-81

OCH3

The course treatment affords

of hydrolysis

503 and 504,

respectively_

The boron of several replacement (R”‘X:

iodide

addition ethanes

vinylsilanes

[475],

borate

complexes

synthetically

useful

R” = CH3) followed

and benzvl

Similar halides

505 quent treatment

replacement

yields

by copper such

Thus,

of alkyl

halides

on 506 follonied

507 [478]

and 1,2-diarvl-

chloride

and basic

hydrogen peroxide

Subseaffords

510. SPh f R’ 30-C-R I SPh

Li RC(SPh)2

510

509

508

Yionane ate complex 511 has now been found and epoxides

/U

II/-

506 507 have been condensed with SOS to give 509 [430].

with mercuric

alcohols

is converted

511 in the presence

of methanol and lithium

Reagent 511 al.so reduces

to cis-

aldehydes

between isomeric

capable

of reducing

In the former case,

14821 to alcohols.

methylcyclohexanone

discriminates

acid

respectively_

irialkylboranes

[481]

has been replaced intermediates.

by the addition

(R3BCii3)-Li’

secondary

fhus,

and aqueotis hydrochloric

hydroxide

505 [477]_

of acrylonitrile

501

502 depends upon the pH [476].

nther examples are described_

lithium

to give

on 502 (!? = Sis,

affords

R

of borate

of 502 with aqueous sodium

using cuprous

&

/i

O/CH, 5 530

393

ox-

OH

. -., .Y iJ=

to

5CKl[475]_

ketones

example,

and trans-4-methylcyclohexanol

selectively

ketones

for

like

methoxide,

respectively

in the presence Z- and 4-heptanones

4by

[481].

of ketones, [481],

and

by

60

-reduces

aromatic

and aliphatic

tions,

respectively

[482].

epoxides

act-l-y1

chloride

systems like

ketones with lithium

oosi-

such reductions

formed by reaction

of cis-bicyclo[3.3.0]-

512 in 1976 describing stereoselective trisiamylborohydride

with triethylborohydride

[435]_

[484], The latter

513 reductions of cyclic

and reductions reactions

of alkyl

are useful

tosyl-

in the

of alcohols_

deoxygenation

Aluminum ate complexes 514 (R = Sii) silanes

and used in the synthesis

hindered

after

513.

x 511 Reports appeared a:es

remaining

It has been conveniently

has been shown to be 512 [483]. of 511 with acetyl

at the most and least

The organoborane

continued

with methyllithium

515 [486,487].

to be investigated_

followed

Other alkylations

by alkyl

Thus,

halides

were also

[487.488]_

reactions

leads

The use of epoxides

to ally1

alcohols

R’

R

instead

on compounds 514

sSi

nun, and lithium

in such

R’ /R’

OH

515 517 has been prepared

in the presence

LiA1(SiZ)4

R3

H

R’

514 alanate

substituted

halides

of alkyl

R “I ,-I-I

Finally,

afford

516 [489].

/ (i-C4Hg)2Al

of

(R-X) gave vinyl-

effected

where R = phenyl , butyl , and hydrogen to stereospecifically ethylenes

treatment

516

517

from chlorotrimethylsilane,

alumi-

of mercury [4901_

LITHIUM-HALOGEN EXCHANGE REACTIONS

9.

A variety derivatives [491]_

of o-haloarylimines

by n-butyllithium,

Hydrolysis

518 have been converted thencoupledto

of 519 gave dialdehydes

to their

519 by various

copper

o-lithio reagents

520_

R

518 Low temperature

‘sHllN

d 519

halogen-metal

exchanges

520

on isomeric

bromobenzoic

acids

and derivatives continued to be described in 1976. Thus, o-bromobenzoic acid wds converted to its dilithio salt 521 and condensed with ketones to afford

61

spiro

systems like

525 [495]

522 [492].

were similarly

Lithio

prepared

derivatives

523 [493],

524 [4?4],

and condensed with a varietv

and

of electro-

phiies.

522 R

521

523

c:i

ii 526 525 dibromo526 has been formed from the corresoonding

524 Cyclobutabenzyne bromoiodoaromatics

by treatment

trapped with furan or allowed present

in the reactions

and lithium certain

of

with n-butyllithium to dimerize.

diphenylarsenide

[497],

“Umpolung” reagents of the corresponding sation

for

with lithium

quinones

o-silylarylamines

like

gave derivatives

by reactidn and vinyl

of alkyllithiums bromides

treatment

Simple conden-

528

reagents [5013_

[SO33 have been prepared

by treatment

14991.

528.

527 Alkenyllithium

with

[498].

527 have been prepared

bromo compounds with n-butyllithium

with electrophiles

were also

diphenylphosphide

and were employed in condensations

to afford

and

Benzyne 526 was .

Genzyneintermediates

1,2-dibromobenzene

silyimethyldialkylamines

[496].

like

529 have been prepared

at low temperature Polyhalovinyllithiums

similarly

of 532 (R = aryl)

stereospeiifically

with vinyl like

by lithium-chlorine

with organolithiums

affords

iodides

[SOO]

530 [502,503]

and 531 In contrast,

exchange. lithium

arylacetylides

[5023.

R\

H

RA

Li 529

Other linsaturated included give

F

Cl

FH

ii

530 lithium reagents

533 which condenses

# Cb

in the synthesis

aldehydes

-F

R

-Li

FH

Cl 1 532

531 prepared

with carbonyl

c-methoxy-a.E-unsaturated

which is useful

F

by metai-halogen

exchange have

containing compcunds to ultimately (534) [504] , cyclooctatetraenyllithium

of bicycle-octatetraenyl

[SOS],

and various

lithium

acetylides

534‘made from l-haloacetylenes

and n-butyllithiun

[5D6].

OCH3 r./~~‘-__

---2

Li

Li 533

534

In the area of saturated converted

to benzyllithium

dibromide

to give

similarly_ lithium

halogen

compounds,

o-bromobenzyl

537 by n-butyllithium;

a bibenzyl

On the other

535

derivative

hand, o-bromobenzyl

536 couples o-Iodobenzyl

[507].

chloride

539 which has been condensed with a variety

Eromophenyl )ethyl lithium

bronide

536 is

with starting bromide behaves

538 is converted

to ary?-

of electrophiles.

bromide and y- (o-bromophenylIcthy1

chloride

also

-f-(0afford

arvl-

derivatives-

536

and trans.-iodotosylates

given

the corresponding

tally

[508].

an unrelated

Similar paper,

lithium

results certain

of dibromo orecursors

539

538

537

Treatment of cis-

reagents

klhich cyclize

were obtained rotanes

540 Gth

like

n-butyllithium

has

to 541 stereospecifi-

on the corresponding

542 have been prepared

4-enes.

In

by reaction

1ike 543 with ohenvll ithium f509].

\I:t

541

540 Finally, to carbenes

dichloro

derivatives

er

have been converted

Cl

XEOUCTIORS ADD RADICALADIOI15 A review article

asxnonia solutions tion

543

by methyllithium. Cl-,

lo_

542 544 [SlO] and 545 [Sll]

, D&a

dealing

and related

with reduction

of heterocyclic

reagents

arrived

to its

tetrahydro

too late

compounds by metal-

for

inclusion

in Sec.-

derivatives

546-548

in amnon-

t [512]. The reduction

of biphenyl

63

ia has been studied of 546.548 Possible

cis-

fected

of anthracene

and trans.-549.

yielded

Reduction dihydro

[514].

increased The latter

of fluorene 552

compounds arose

constitute

disilylated

For example,

short

Reductive

from metalation

amount

methylation

of

alcohol

a simple

synthesis

acid

periods

gave

tetrahydro

of fluorene

rea-

lithium,

mostly products

with lithium/-

and 9,9-dimethyl

of the 9-hydrogen

553 E ring of yohimbane 555 has been converted

of o-methoxybenzoic

benzene,

in ammonia for The small

an-

of silylatins

550 and 551.

554 and o-methyl-

by lithium/arrmonia/i-propyl reductions

corresponding

of i49 was ef-

in THF affords

[516]_

time.

bromide afforded

and sodium in THF has

Dehydrogenation

in the presence

[515].

by lithium

and 553

with increasing

552 The aromatic

the

afford

of benzene derivatives silylhydroaromatics

derivatives

ammonia/methyl

(556)

and 39% with magnesium.

in ether/benzene

respectively

i thium/TMEDA to

Qeduction

also

by lithium

and 1,3-dichlorotetramethyldisiloxane

ilar

The combined yields

the metal [513].

12.5:: with sodium,

were 18: with lithium,

by n-butyll

tracene. gents

of

mechanisms are discussed.

Reduction given

as a function

folloued

554 to a cyclohexanone

by aqueous acid

in the presence

of Z-alkylcyclohexenones

derivatives. atoms of the oarent

of alkyl

557 [518].

[517]. halides

Sim(9X)

64

H02C’

I .; OCH3 557

Improved 559,

procedures

respectively,

for

involving

the

conversion

the

use of

of

indole

ester

has been

ring opening,

and ring

reclosure

with liihium/aEzeonia/alcohols 563

used to remove the phenolic

from e’-tetrahydrocannabinol

been employed to reduce 3-furoic

aIS.

[522]_

The overall

to a butyryl

Reductive

boxyl

hydroxyl group pasked Lithiuc/azmonia has

[SO].

to 560 and 561 via E-elimination,

Thiophenes

to afford,

sequence

after

represents

like

562 have been treated

hydrolysis,

aninoketones

the transformation

like

of a thiophene

methylation

563

562

of 564 and its

gave 565 and 566, respectively group controlled

group was introduced group.

acid

[521].

561

try of the 9-carboxyl methy

pub-

group.

560

methy? iodide

558 and been

559

558 Lithiun/amonia

to have

H

H

as a phosphite

and carbazole

fithium/armonia/r!!ethanol

epimer by lithium [523].

that of methylation

from the side

in THF followed

Clearly,

of the molecule

by

the stereochemis-

at C-8 since opposite

the

the car-

C02H

‘CH3

Menthone (567)-isonenthone tively

to menthol

Other reducing

566

565

564 (568)

mixtures

(5G9) and neomenthol

media and hydrogen

(570)

including

systems studied,

in the presence

have been reduced stereoselec-

only

by lithium/ar;mocia

sodium and potassium

of ruthenium,

rhodium,

[524].

in various

and platinum,

were

not stereospecific.

iin +:-unsaturated duced

of

IO-epieudesmane

bromide to afford,

among other

from C-alkylation, of

like

ketones

and a tetrahydrofuran

intermedeo:

has been reductively

572 has been converted

the presence

an epoxide.

570

or lithium/ethylenediamine

sesquiterpenes

Methyl benzoate

ter

ketone,

by lithium/ammonia

propiophenone

569

568

567

have been re-

as part of the synthesis [525].

ethylated

by lithiun?ar;monia/ethyl

ethyl henzyl ether from 0-alkylation. products, and 571 from ring reduction [526]_ Ally1 es-

to allyllithium

to qive -i-alcohols

CH3Cil

reagent

573 by lithium

in THF in

r527]. _ Li+

‘\L ’

K’

‘\,

!

‘H

571 Tandem alkylation-reduction cyclopropyl sequence

aromatic

hydrocarbons

572 has now been applied [528].

The process

573 to the synthesis is illustrated

574 to 576. 0

OLi

574

575

576

of a-

by the

66 Related

to the above,

by lithium/amnonia the presence

cyclopropyl

phenyl ketone has been reduced

Subsequent

[529].

of amnonium chloride

reduction

to 577

of 577 by lithiumfamnonia

and sodium benzoate

affords

in

578 and 579,

re-

spectively. OH

OLi

I.

In contrast. [532]

cyclopropyl

are cleaved

the cyclopropyl

ring

The conversion

tion.

reduction

of

several

chloride

tions

the cis

530 [530,531] like

and 531

532 and 533, re-

several

organic

halides

to organolithiums

(and bromide)

other

products

534 was converted

in which

are presumed to have proceeded

tion

of 587 with n-butyllithium

tion

of configuration_

(587)

and heptenes

and trans hydrocarbons

reaction

with lithium

was not stereospecific

were obtained

via vinylic

[533].

[534].

in TtiF to since Such reduc-

radicals.

gave the respective

2

men-

586

585 reagents

deserves

to the lithium

536 via a cyclization

of E- and Z-4-chloro-3-heptenes

the vinyllithium of

products

yielded

then condensed with 525 to give

Reaction mixtures

to give

also

584 afford

in compounds like

has been opened.

Thus, allenyl

reagent,

rings

by lithium/ammonia

The latter

spectively.

579

57.3

577

In contrast, reacvinyllithiums with reten-

-‘\ 587

Lithium/awonia stead of the desired an electrochemical

reduction propellane process-

of 588 gave mostly 589 [535].

Similar

norbornane results

and a dimer inwere obtained

by

6i

589

588 ,+ChJoroenamines

590 have been converted

magnesium in solvents reaction

like

with deuterium

oxide

enanine 594 was observed

59G Various :Lnitrosamines

by lithium

bonds have been cleaved as illustrated r. --\

by radical

alkyl

ium instead

and ethyl

iodide

potassium

The C-alkylations than by nucleophilic

56

‘SH13

of adducts

afford

with alkyl

and the solvent

are said

halides [540].

598 and 599 (ortho

and cesium ketyls to occur

give

via initial

[gJq” 599

and para)

to all

to the use of

have been studied

600

Jith-

as-

the lithium

but no 600 or 601. of these products.

electron-transfer

)Af

to alkyllithiums from 597 and the

For example,

and para)

rise

displacement_ 0

(ortho

References p

i -\

converted

j.

$)-);I

(

L-I

ketyls

Carbonby Jithium/-

of 595 to 596 [538].

derived

cation

593 secondary

[5373.

contamination

of benzophenone

R2?r-\

in good yields

596 have been quantitatively

595 chlorides

of the alkali

In contrast,

)i-i/

[539]_ The success of the method is ascribed of sodium and to the steric bulk of 597_

Reactions a function

hR2

?,R ‘2

hydrocarbons

and

after

Deuterated

592, H=H 594, H = D to the corresponding

‘*-C6HJ3

anion 597 without

alkyllithiums

593.

and magnesium in ether

to give

by the conversion SeCH3 Xyl

‘L,’

Various

_(

>

591 have been cleaved

amines in very low yields

ketyl

were enamine 592 and diner

\.-iLi /; \ hR2

2

ethylamine

sodium,

The major products

with sodium and magnesium only. H

>;;;c:,

sefenium

to 591 by lithium,

THF and hexane [536].

steps

,;a 601

rather

Overreduction tyienic kali

ketones

metals

has now been avoided

like

in liquid to azo/-

of steroidal

naphthalenes

Lithium naphthalene

ammonia [541].

in a new synthesis

ployed

nitrobenzene

in the cvclization

602 to 603 by using alkali

of (?)-sempervirol

instead

has also

aceof al-

been em-

15421 and in the reduction

of

and__azoxybenzenes [543]. -./. .t>

_/-

-J1

_ ..I,+

t 111

, i .---

IA/

‘\ aH 603

602 ll_

REACTIONSWITH INORGANIC Several

like

AR0

I-cyanocarboranes

and m-carboranes

ORGANOMETALLIC

COMPOUNOS

have been prepared

with phenylcyanate

604 have been synthesized

[545].

of 606 with n-butyllithiom

by reacting

605 with certain

rivatives

papers appeared

carboranes

(8lOHl2)pdjphenan) 606

in 1976 describing

of germanium, tin, compounds [547]

the preparation

Carbanion

607 [547,548].

and lead to give and benzyl

and reactions

607 has been condensed

608 [547].

bromide [548],

Reactions

and of lithium

of de-

of 608 are discussed_

608

607 Other boron-containing methoxyboron chloride.

molecules

lithium,

prepared

and silicon

using

SiCMOCH3),14

into

the details dilithioalkanes

except of

[SSO].

610

611

metals,

layered

and Ta. X = 5, Se, and Te [551]. cases

n-butyllithium

and titanium

has been employed to

MX2 compounds where M = Ti, A limiting

VSe2 which gave Li2VSe2.

the preparation

and 610 from

CH3-0-CBIOHIOCLi

In the area of transition lithium

were 609 from di-

[549]

(Cii3-~-CB10H10C)3P

609

intercalate

lithium

tetrachloride

611 and bis(methyl-o-carboranyl)chlorophosphine

in all

lithium

605

bis(boryl)methide

607 with carbonyl

o-

complexes

606 has been made by treatment

(Ph3P)21r(CO)Cl

604

with derivatives

C-lithium

iridium(I)

in THF [546].

(Ph3P)21r(CO)(c-carb)

Two full

by condensing

New stable

[544].

An anion of phenanthroline-containing

of lithium

.i

composition A full

of titanium(IV) dichlorides

[f&G?].

Zr.

Hf. V, Nb,

of LiMX2 was obtained

paper appeared describing

metallocycloes.

like

The characterization

612 from and

69

reactions

of

prepared

the metallocycles

from alkyllithiums

dicyclopentadienylzirconium methylzirconium

(613)

Other compounds in this

is discussed. included

and hafnium dicarbonyls and zirconium(W)

[555],

[554],

614 [556].

*p3

lithium

pounds similarly lun [559],

prepared

I t-

1

CH3 -2

615 have been prepared

and niobium(V)chlor

include

hexacoordinated

_i

I

614

compounds like

cyclopentadienes

y3

! Zr (ii--fi+O

613

Cyclopentadienylniobium tuted

[553],

bis(fluorenyl)di-

amides like

(C13H9)2Zr(CH3)2

612

family

tetrakis(pentafluorophenyl).zirconium

from- substi-

[557,558]_

pentamethylniobium

[559],

tantalum complex 616 [560],

Other com-

pentamethyltanta-

and tetamesityl

com-

pounds 617 (M = V, Cr) [561,562]. ,CH3 (CH3-@&--+~Li 3 617

616 615 Carbene complex 618 has been synthesized reagents,

phenyllithium,

then trimethyloxonium

complex 619 has been prepared and lithium

cyclopentadiene

hexacarbonyl

, lithium

ium and tungsten species

like

/

--ArCr(C0)2(C

\

[564].

and triethyloxonium

621 have been condensed

action

fluotoborate

reagent

chromium

[565]_

Chrom-

with organ01 i thiums to give

0CH3

I Ph

/OCH3

.OCH

)

(CO)5Cr(C$Ph

(co)5w=/il \ Ph

3,

Ph 622 more papers appeared discussing

of molybdenum and tungsten Thus,

full

with molybdenum(II1) to afford

from

619

621 Several ple bonds.

Carbyne

and 623 [567]_

‘Ph

properties

[563].

tungsten-bromine

Compound 620 was prepared

618

(CO)$l(C

fluoroborate

from the corresponding

dithiane,

complexes

622 [566]

from ?-aryltricarbonylchromium

625 [569]

papers describe chloride

to give

and 626 [570].

of 626 with methyllithium

623 structure,

the preparation,

compounds comtaining the reactions 624 [568]

metal-metal

of lithium

yields

dial_kylamides

and with tungsten(IV)

Other examples are cited. 627 [571].

A related

and multichloride

In addition, condensation

reof

i0

anti-626 tion

with lithiomethyltrimethylsilane

of configuration

at tungsten

Mo2(NlMe2)6

U2(NMe2)6

has been shown to occur

via a bimolecular

four-center

with retenmechanism 15721.

(Et211-7%

H2C12(NEt2)4

CH3

Dihydrides the latter acid

reacts

chlorides,

627

626

625

624

to give tetramer 629; 628 (El = MO, H) react with n-butyllithium at the transition metal with alkyl halides, as a nucleophile esters,

and benzaldehyde

to afford

metal-carbon

systems

like

63D [5731_ n5-cp

n5 -cp

Y.M/H

3 -Cp’

?;_C/

H

’

‘5

((C5Hg12MHLi14

Other chemistry

in this

631 from hexamethyltungsten more fluorines phenyilithium

family

included

the preparation

and methyllithium

of 632 by organolithiums across

and tertiary

630

629

628

the azo linkage

[574],

[575],

of tungstate

the replacement

the stereospecific

of 633 [576],

and I-arylation

of

of ethers

PhHC16Li

633

632 Manganese compounds 635 fR = CH3, Ph), lithium

with 636, represent

carbene

is stabilized

complex (637)

carbene

as a ligand

has been obtained

/

complexes

634

prepared

by reaction

where a dialkyl-

to a metal atom [578]. similarly

MO calculations

C5H5(C0j2Re=C \

have been performed

that these

of nucleophilic reactions

at coordinated

on 638 and 639 to determine

attack

are frontier

rhenium

CH3

637

636

the site

of methylor arylalkyl-

An analogous

3 635

-

[579]_

C5H5(C0)2MnXR

C5H5(CO)2Mn=C

that attack

of one or

amines by 634 [577]_

631

.cluded

ion

addition

[CsH5Mo(C0)2?W]PF6

control

‘P .

on such species rather

CO is much more likely

[580].

factors

than charge controlled for the acyl

which

It is conspecies

and (639)

‘71 than for

the carbene

condensed Protonation cule

complex

(638).

Experimentally,

with 640 and 641 at CO to give of 643 afforded

the enol

642 [581]

methyllithium

has been

and 643 [SSZ],

respectively.

tautomer of a metalloacetylacetone

mole-

[582]. OCH3

/ (COJ5CrC

0 (CO)5F!n/K

“ii

(COj5Rn /Y

?

Ph

3

638

639

64’3

-_: (COj5Ze/-\ 642 The first thesized

acylsilane

derivative

of a transition

from 655 and triphenylsilyllithiun

metal,

644,

has been syn-

[583]_

; (C0)3jP)2ReN

(CO),Qe(P,)

‘SiPh3

644 Other rhenium and manganese compounds prepared dirhenate(III)

(646)

cctamethylrhenate(Yif and allenylidene

fron methyllithium

_

645 in 1976 include

and rhenium pentachloride

(64E) fro:n methyllithium

octamethylor 647 [5%].

and hexanethylrheniun

compound 649 from t-butyllithium

and acetylene

[535],

complex 650

[5863. Li2Xe2(CH,), JO

Li2Re(CH3)8

Re,(KPh),Cl2

646

648

647

649

650 * ferrate

Lithiuncycloheptatrienyltricarbony~ various

metal

carbonyl

halides

to aive

Mn, Re. X = 3 and 14 = Rh, X = 2)

verted

to bisffulvalene)diiron

ferrocenes prepared

[589]

[587]_

(654)

(651)

has been reacted

hetero4inetallic

complexes

Dilithiofulvalene

by iron(I1)

chloride

(653)

by treatment

of appropriate

lithium

has heen con-

[588].

and 1,1’,2,2’,0,4’-hexakistrimethylferrocene cyclopentadienes

with

652 (M =

[590] with

Polymethvlhave been iron

72

bromide and chloride,

respectively.

(C7H7)Fe(CO)3Li 652

651

653 654 Two related been prepared [591]

bis(cyclooctadiene)cobaltlithium

from 1,5-cyclooctadiene(cyclooctenyl)cobalt

and from cobaltocene Iridium

respectively. responding ophilic

iridium

nea protecting

and lithium

complexes

chloride

reactions

of

like

group for

and aryllithiuns

peptide

ethylene

[593].

syntheses

complexes

alkylphosphine,

657

with ;-MO-C bonding,

reaction

and ethylene

affords

illustrated

of this

same nickel

compounds like

reagent,

[Li(THF)4]C[Ph2P

dinitrogen-nickel

in ether

phenylsodium

nickel

[SSS].

di-

Xi(C2H4)2

/ \_

?iI (C2QZ1-

complex 660 has been prepared

phenyllithium.

by reaction

with phenyllithium/phenylsodium

Ethylenebis(phenyllithium)nickel

compound have been synthesized

reagent.

lithium

659

all-rrans-1.5.9-cyclododecatrienenickel nitrogen

have

TYEOA, and

659 [597].

658 “Side-on”

by 658, (RLi),

organolithiuns

[Li (2T?lEDA)]+[PhNi (C2H4)2]-

nucle-

for a

(CO)Ir(Ar)(PPh3)2

(C8H12)2CoLi(THF)x

Similarly,

[596].

Two papers described as model reactions

656 (0)

[592],

from the cnr-

[59$.595]_

from bis(cyclooctadienyl)nickel,

been prepared

of cyclooctadiene

657 have been synthesized

655 nickel

and phenyllithiun

in the oresence

lithium-cobalt-phthalocyanines

(C,H12)2CoLi(LiPh)-2(C2H5)20

hovel

compounds 655 and 656 have

phenylsodium.

and the

by reaction

of

and ethylene

of

and

related

the same triene-

[599].

660 Other compounds in this bony1 dianions

like

family

661 by reduction

recently

described

of platinum

include

chloride

platinum

car-

systems or pre-

'73

formed platinum

carbonyl

from the corresponding kel chloride

systems by lithium chlorides

from a complexed

and metallocycles

[602],

nickel(II)

like

[600],

platinum

complexes

and perfluorophenyllithiun chloride

[61)1],

and lithium

663 from the platinum

chloride

like

662

benzylnic-

tribenzyltin and 1,4-dilithio-

butane [603] _ Pt3(CO)6Li2

A variety

of

thorium derivatives

664 (R = alkyl

pared by reaction

of the thorium chloride

Grignard

[604].

reagents

663

662

661

Ring-bridged

and alkenyl)

derivative

have been pre-

with organolithiums

uranium halides

and

665 have similarly

CG(C5H4)212U2C15Li (THF12

(qs-C5Hs)3ThR

aJGbJ Lit

665

664

666

Li+

Terbium and holnium compounds 667 (R = t-C4H9) have been synthesized the reaction prepared

of 668 and lithium

by the interaction

di-t-butylphosphide

[606].

of 670 with n-butyllithium Ln(=>?<

667

663

The first

organogold(I)

pared by reaction

complex containin

of perfluorophenyllithiua

tetrasilane

673 may be prepared

I,Cl3

670 a S-donor.

671.

has been pre-

and 672 [6g!?].

metal.

Table,

by treatment

[609].

This same paper describes

with lithium

P’,

672

tetrachloroplatinate

sink.

Ln[-

ClAuSC4Ha

Turning to Group IV of the Periodic

lithium

from

669 has been

[607]_

669

671

potassium

Ylide

)3

(C6F5)A~SC4H3

cyclopentasilane

been

of 666 (G = Cti2, Si Z, n-propyl ) wi.th uraniun( IV) chloride

made by condensation [605] _

The latter cleavage

it has been found that perarylof either reagent reactions

674 or 675 with is said

to act as a

of perarylcyclo-

p\siPh Ph\

--,*ilPh

_‘-

p/-S’i

I

\Pil

‘+Ph Ph

ph5si?h

674

673

Other preparations

of cyclic

silicon-containing

by 676 from 1,8_dilithionaphthalene 6T8 and disilane

ylide

conpoun-!s

are

and dialkyldichlorosilanes

679 16111,

illustrated

[610],

677 fron

and 680 from 681 and dic5lorodinethylsilane

[6121_

(CH3)3P

(CH3)3P

676

677

678

680

681

CH 13 Cl,Si\

; C12Si/

1

CH 3 679 Divalent or,

species

682 (M = Ge. Sn. Pb) have been prepared

from 683 and 684,

s*hen X = Sn or Pb, from 683 and MC12 [613,6147. ZS-

Fi

Sir

ZSi

,Siz J--+l-_(;

‘>-( ZSi

‘\

> _Sl

Sis

682

683

Imidazolidinonederivative aprotic

solvent

reactions

metal to give

that 685 lies

684

685 has been tested

for organometallic

with ketones and lithium It is concluded

‘Sis

for

by reacting

disilyated

its

suitability

as an

chlorotrimethylsilane

derivatives

like

between THF and HVPA in promoting

686 [615].

such reactions.

i5

Other chemistry reagents

the preparation

in this

across

L-6171, the synthesis chloride

group included

the addition

of of

tin

triphenylsilyllithium

lithium

using get-manium(!:‘)

of organolithiums

linkag..e of :-germyl

the nitrile

of 683 from the correspoxding

and the conversion

‘*i_

686

685

Grignard

/Xii:

0

-CH3

nitriles

reagent

and

687 [616],

by trans.-netalation

from 689 and methyllithium

cyclopentadiene

[618],

to cyclopentadienylget-manium

tri-

chloride [619]_ :Si

3EeCH2CC

(C2H5)

like

(CO)4CoSiPh3 l-i

687

688

An interesting derivative fected

691 and dichlorodimethylsilane

using

SilSiCl3

689

690 has been obtained

dispirotetrasilazane

The synthesis

[629].

and n-butyllithium

from tetralithio

followed

by addition

of 691 was efof aniline,

then

more n-butyllithium.

691

690

Treatment of silicon-nitrogen cyclic afforded 622]_ yielded

systems_

693a-b apparently In contrast,

694 presumably metalation

to be prepared

Rcferemesp.58

R’

= Ph)

via methanide migration

692c (R = i-C-&.

695 with n-butyllithium similar

systems 692a-c

Thus. 692a (R = t-C,H,.

via a silicenium

and 692b

ion [622].

gave 696 via the latter

(R = R’

to a silicenium

R’ = Ph) with the

of 697 gave only N-lithiation,

[624].

with n-butyllithiun

smaller

Reaction

route

[623].

the first

also

gave

= t-C4Hg)

ylide

i-propyl

of silyl On the

[621, grouo

system oth
hand,

such organometallic

76

t-c&,

Y

:

Si-R’

I

I

X--

Zi-N-:i-NHt-C4Hg

; Si-

I= 692a

R’=Ph)

(R=t-C4H9.

692b

(R=R’=t-C4H9)

692~

(R=i-C3H7.

i-C3H7\

p3 N-

IiHt-C4H9 YPh

I

i

TSiL

N-t-C4Hg

694

693a

(R’=Ph)

693b

(R’=t-C4H9)

R’=Ph)

(t-C4H9)2Si,

AF NHt-C4H9

Azosilolines

like

and phenyllithium

697

696

695

698 have

been

synthesized

from

J.

Silylated ate

ter

aldimines

complexes

enamino-tin yields

chlorotributyltin

halides

may now be simply

[626,627] system,

previoulsy 16291.

Zi-N=CHR

with for

described Similarly,

prepared

by treatment

chlorotrimethyl_silane

example,

702-703,

by treating metalloimines

[628].

of The

can be obtained

iminolithium 704 have

in

reagents

bet-

with

been obtained

M+(C2HS)3B-N=CHR

from jR \

CH3--=-N

702

701

Ph

Lit

-YNR 703

new imino-

[6301.

700

SnR3

699

699 (700)

701

metalotropic than

705 and metal

precursors

_Ai_ _/’ - NHR

698

boron

benzyne

[625].

Ph

Ph 704

705

SnR’3

ii Nitrogen-nitrogen with lithium

and Group IV systems.

tetrachloride, reaction

and nitrogen-oxygen

and butyllithium

Thus, reaction

affords

708 L-632]_

have been synthesized Finally,

Several

bis(trimethylsilyl)hydroxylamines n-butyllithium,

(Si)

NOSiz

lithium

phosphinelithium like

like

followed

708 / PhN 1.

OSis

Sir

711

712 have been prepared

by addition

of

by reduction

chlorotrimethylsilane

compound 713 has been synthesized

n-butyllithium

from

[634].

710

Organosilylphosphines

709

[633].

have been prepared

ZiNHOSiz

709

with

(711)

gives

like

and chlorosilanes

707

2

Similar

then hexachloroethane

and chlorotrimethlsilane

706

carbon

707 [631].

tris(organosilyl)hydroxylamines

from 710, n-butyllithium,

phenylhydroxylanine,

been combined

of 706 (M = Si),

aminoisocyanide

of 706 (M = Ge) with an organolithium,

germyldiimine

phines

systems have also

of phos[635].

Silyl-

from 714 and organolithiums

[636].

(Zii)3P

Calculations complexes states these

have been performed

[637] _ The authors

on the activation

conclude

in which the N-N bond is highly states

can be described-as

of nitrogen

in n-iinN

that stabilization

of the electronic

loosened

and that certain

occurring

can occur

from one- or two-electron

of

reduction

of nitrogen_ Diazadiphosphetidines phenyllithium

traphenylphosphonium dialkylamides, or the formation group.

like

715 have been prepared

Phosphineimines

[638].

chloride

though,

affords

like

and lithium

alkylamides

homolytic

decomposition

of N.N-dial kylanil ines,

by treatment

717 have been synthesized

depending

[639].

from te-

The use of lithium

of phosphorus

on the size

of 716 with

compounds

of the alkyl

R

I

CH RH’ 3

P

PC” ‘CT

‘I/--

R Ph P=iiR 3

I

CH3

Lithium diphenylphosphide chloroethenes ethylenes.

to give

depending using

and arsenide

stereospecifically upon the central

phosphinoarsinoethylenes prepared

are also

lithium

chemistry

and chlorodialkylphosphines 720 and organolithiums

mono- or diphosphino-

rivatives

and arsino[640]. %xed compounds

Other Group V and VI

have include

[641 J, sulfur

and Grignard

with 1,2-di-

atom and the stoichiometrv 718 from lithium

cyclopentadienes

compounds 719 from suliurdiimines

reagents

[642],

[643],

722 from nethylalkoxychlorosilanes

?-silylcarbanions

have been condensed

described_

the parent compound and n-butyllithium like

717

716

715

721 from

methyla!koxy(alkylthio)silanes

and lithium

from 723 and n-butyllithium

lithiosulphimide nercaptides

[645]_

of a glucopyranos- 0 have been prepared

Finally,

by reaction

of

[644],

and

sulfur-tin

de-

724 with a py-

ranose bromide [646] _ Rn=S-R

I

R’ 718

AH

W=S=NR

(CF3)2S=:lLi

720

721

‘R

719

R’ I

R”

RSeXSiRY’

CH30-Si-SPR

R3SnSLi

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12.

724

723

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